The Ibrox side were pitted against the Reds, Napoli and Ajax in Thursday's group-stage draw in Istanbul.
Rangers are back in the group stage of Europe's elite competition for the first time since their financial meltdown a decade ago.
And Arfield is particularly enthused about the prospect of facing last year's beaten finalists Liverpool, with a huge Gers support expected to descend on Merseyside when they meet at Anfield.
"The three of them are amazing, amazing cities, so we're definitely looking forward to going to them, but the one that captures the attention is the Liverpool one because it's closer to home and we know our following there is going to be sensational," said Arfield.
"That's the one we're probably looking forward to the most. They have been finalists for numerous years and they're one of the best teams in the world, and now we can show what we're all about."
Having reached the Europa League final last season, Arfield is adamant Rangers will not be fazed by the quality of opposition they face in the Champions League and is confident they can make their presence felt in Group A.
"As always, we think we can be very competitive," he said. "It was a great draw for us with a lot of big dogs in there, which when you get to this stage of the competition there's going to be.
"It's an exciting draw for everybody and we want to be as competitive as possible."