Foreman IMO - he was every bit as feared/revered as Liston, & he had bombed out 2 fighters that already beat/troubled Ali.
They were all huge wins. Liston being a huge surprise shocking the world. Foreman was similar but Ali was shopworn being the conventional view at the time. The Frazier fight was different. People expected Ali to win going in but it's what happened in the ring that makes this perhaps Ali's moment. What he had to overcome in the ring that nite. Foreman and Liston were both scarier going in but I guarantee by round 5 neither of them had Ali praying to Allah the way he was in the Philippines. Ali was playing with his food by round 6 in Zaire. Ali showed legendary toughness and courage that the gritiest Bareknuckle brawler from 1890 would have respected in Manila.
Liston. Nobody knew Ali at that time. At least with Foreman - people knew his track record that he was a great fighter.
I’d have to go with Foreman although Liston 1 does run it close. In both he was a huge underdog against two opponents who were almost considered unbeatable certainly against the contenders who were out there.
I would say Foreman--Ali had to use his mind power to win that one--couldn't rely on his physical gifts and youth as he was able to do in the 1st Liston fight. (And Foreman in October 1974 was regarded as invincible as Sonny was in February 1964.)
Frazier-Ali II was a better win than Manilla, and even then the win was somewhat spoiled by excessive holding. Fight of the Century Joe was Ali's only chance to beat what was the best version of Smokin' Joe anyway. Gotta be Foreman by virtue of it being a show of grit, extreme faith, and that subtle defensive wizardy Ali was capable of (with Archie Moore saying after the fight that George failed to realize he is in the ring with an escape artist of a highest caliber.) Liston I was a huge upset as well, though Ali was younger and stylistically harder for the aged Liston in hindsight. Foreman-Ali is still outshined by the impossible decision Pep scored against a thriving version of Saddler over the dreaded fifteen rounds (and Sandy with his power, mauling, and conditioning, was an absolute nightmare to go against in the last five rounds.)
I have to go with Liston. Ali was a 7-1 underdog (as opposed to 4-1 against Foreman) and it was Muhammad's big break as he won his first championship. The Foreman victory is second, though.