Betting on Group F is all about whether you trust Manchester United enough and perhaps specifically their manager, Ole Gunnar Solskjaer.
Meanwhile, Chelsea look set to get their Champions League defence off to a smooth start in Group H
Group E - Bayern Munich worthy favourites
Bayern Munich - at around 4/7
Barcelona - at around 15/8
Benfica - at around 9/1
Dynamo Kiev - at around 25/1
Bayern have added Marcel Sabitzer to an already-strong midfield, while David Alaba's departure is compensated by the arrival of Dayot Upamecano, who is touted for a bright future.
Up front, Robert Lewandowski is about as close to guaranteed goals as they come and it's not hard to see him adding a few more to his huge UCL tally against Benfica and Dynamo Kiev here.
Benfica are coming off their worst domestic finish in 12 years, while they also failed to make much of an impact on the Europa League, losing to Arsenal in the last 32. Joao Mario, a title winner at Sporting Lisbon last season, improves them. Roman Yaremchuk and Soualiho Meite also look useful signings so the Portuguese do at least have an outside chance of upsetting the big two.
It remains a long shot though, albeit not as long as Kiev's chances. They've not been beyond the group stage in this competition since 2015/16 and theirs remains a largely home-based squad, featuring several of the players humbled by England in the Euro 2020 quarter-finals.
Barca still look likely to provide the biggest challenge to Bayern. However, with Lionel Messi gone, it's not hard to see this UCL campaign being a tough one to negotiate for the Catalans.
If you do feel the group will be decided in the games between Bayern and Barca, it's worth remembering that the Germans triumphed 8-2 when they last met just over a year ago. Since then the Spaniards have lost their greatest-ever player and endured turmoil on and off the pitch.
While their price is hardly mouthwatering, a Bayern team only narrowly beaten by Paris Saint-Germain in the quarter-finals last season should have enough to top this section.
Group F -Villarreal can topple United again
Villarreal - at around 5/1
Manchester United - at around 8/13
Atalanta - at around 14/5
Young Boys - at around 12/1
Following the acquisitions of Cristiano Ronaldo, Raphael Varane and Jadon Sancho, the current United squad is the club's strongest since long before Sir Alex Ferguson retired. However, Ole Gunnar Solskjaer still looks a poor man's version of Klopp, Tuchel or Guardiola - all Champions League winners as managers.
Villarreal and Atalanta both look dangerous threats to United and it's not hard to envisage the English side becoming embroiled in a three-way battle for the two qualification slots. Yes, United are probably worthy favourites but should they be virtually the same price Bayern are in their group? For me, the answer is no.
Villarreal beat United in last season's Europa League final, a fact which immediately makes their odds of around 5/1 about winning the group look a tad large. Bournemouth winger Arnaut Danjuma was their big piece of summer business - admittedly put rather into the shade by United's deal for Ronaldo - and they still have last season's major goal-getter, Gerard Moreno, not to mention a tight defence.
They are my preference with which to take on United, ahead of Atalanta. Gian Piero Gasperini's men were lauded for their attacking approach a couple of years ago but last season they proved a bit of a disappointment in this competition, despite a win at Anfield. They were thrashed by Liverpool in the home game and eventually bowed out to Real Madrid in the last 16.
Young Boys, the Swiss champions, look a little out of their depth here. Perhaps their biggest asset is their artificial pitch which has long proved awkward for visiting teams. The biggest part they'll likely play in determining the group winner is by taking points off a visiting side to Berne.
Group G - Sevilla decent price in a tight group
Lille - at around 3/1
Sevilla - at around 11/8
Red Bull Salzburg - at around 5/1
Wolfsburg - at around 5/2
This looks the most competitive of the eight groups - and the bookmakers agree, with Salzburg, the outsiders of the quartet, only at around 5/1 to win the group.
It also contains the only odds-against favourites, Sevilla, who do look the team to beat. They've got the influential Papu Gomez in for this year's group stage following his January arrival from Atalanta, while they already had plenty of European pedigree having won the Europa League on numerous occasions, most recently in 2020.
They were on the fringes of the Spanish title race for most of last season, conceding just 33 goals in total - only the two Madrid giants had a better defensive record.
Lille were the surprise French champions last season but as with any surprise package these days, the vultures have circled to take away some of their leading talent, including manager Christophe Gaultier and midfielder Boubakary Soumare, now at Leicester. They've not started this season well with their defence conceding nine goals in their opening four Ligue 1 games.
Salzburg have started their domestic campaign better but have also had to deal with bigger clubs coming in for their stars. Both Enock Mwepu and top scorer Patson Daka have departed for the Premier League, leaving sizeable holes to fill.
Wolfsburg look like they could be the closest challengers to Sevilla. They started the Bundesliga season with three straight wins, building on last season's impressive fourth-placed finish, but they've got the issue of lacking Champions League experience in recent years - this campaign will be their first in the UCL in six years.
All things considered, Sevilla look a decent price.
Group H - Top two to have it all their own way
Chelsea - at around 8/13
Juventus - at around 5/4
Zenit St Petersburg - at around 16/1
Malmo - at around 50/1
It's hard to argue against Chelsea, the reigning European champions. They've hardly put a foot wrong since the arrival of Thomas Tuchel, the German manager has turned the Blues' fortunes around. He primarily made them much harder to beat but he's now added a world-class striker in Romelu Lukaku to bolster their attacking department.
Juventus, regarded as their biggest pool rivals, have just lost star man Cristiano Ronaldo - Moise Kean returns having failed to make the grade in the Premier League - although at least improvements seem to have been made off the pitch with the questionable decision to appoint Andrea Pirlo on the back of his playing achievements now a thing of the past.
Instead, Max Allegri, who enjoyed plenty of Champions League success with the Old Lady, twice reaching the final, is back at the helm and looking to return them not only to the top of Italian soccer but also of Europe.
Zenit and Malmo are likely making up the numbers here. The Russians made a familiar group-stage exit last season. They've progressed to the knockout rounds in just three of their previous eight appearances in the group stage.
As for Malmo, they've already succeeded in this season's competition given they had to start in the very first qualifying round - they played their first match on the same night England beat Denmark in the Euro 2020 semi-finals. Jon-Dahl Tomasson's side are struggling somewhat in their Swedish title defence and it's hard to see them making a big impact at this level.
For those who like to put a multiple bet together, the Chelsea, Sevilla and Bayern treble looks juicy at just under 7/1.