While the South African golfing legend defended Phil Mickelson after his decision to get involved with the Saudi-backed tour a few months ago, he is far less understanding of younger players going over at the height of their careers.
"I wouldn't take a billion dollars for my nine majors on both tours," Player said in an interview on BBC Radio 5Live.
"I worked hard. I had desire. I travelled the world. It was an education, I met wonderful people.
"How can you ever be a champion playing a tour with 54 holes and no cut?
"What sort of tour is that? 54 holes, no cut, a team event nobody understands.
"It's a tour for people who don't have confidence in their future. They don't have the confidence they can be winners.
"It's never going to compare to the regular tour. No chance."
Australian world number two Cameron Smith recently became the latest high-profile LIV Golf signing and Player can't fathom why the reigning Open champion took the offer at this stage in his career.
"Here's a young man I really thought was going to be a superstar," said the 86-year-old. "Now what sort of future does he have?
"Will he be able to realise this great dream of being a champion? I don't know.
"I don't blame [Henrik] Stenson for going. He had no money, so he had to go.
"But this is a potential superstar. I think his advisors have given him the wrong advice."
Player was adamant there should be serious consequences for the defectors.
"They've declared war on the PGA Tour," he added. "They must not expect to play in the Ryder Cup, the Presidents Cup, play in the majors and all those things.
"You can't have your cake and eat it. That's the bed you've chosen, that's the bed you've got to lie in."
Asked if he thought LIV could ever overtake the PGA Tour as the top circuit, Player replied: "Not even a chance."
Icy reception awaits at Wentworth
Meanwhile, DP World Tour CEO Keith Pelley has revealed how the tour will be handling the presence of a number of LIV Golf rebels at next week's BMW PGA Championship.
The 18 players can expect a pretty icy reception at Wentworth, according to a memo from Pelley obtained by The Golf Channel.
"They will not be given any on-course competitive disadvantage - i.e. unfavorable tee times - but they will not be required to play in the pro-am on Wednesday and will not be in TV featured groups," Pelley wrote.
Recently-crowned FedEx champion Rory McIlroy and US Open winner Matt Fitzpatrick are among those who have voiced their opposition to the presence of the LIV rebels at Wentworth.
They are currently permitted to play due to an injunction that temporarily prevents the DP World Tour from suspending them from competing in its tournaments. A full legal hearing on the matter will be heard next February.