Veteran Hall of Fame jockey Gary Stevens piloted the five-year-old horse past the celebrated field down the home straight before holding off a late surge by Will Take Charge to win America's richest horse race by a nose.
Declaration of War finished third a head adrift in front of more than 58,000 fans watching in glorious late afternoon sunshine.
Game on Dude, who had finished a disappointing seventh after also going in as the favourite last year, had won all five of his starts this year and was in contention coming off the final turn before fading badly into ninth place.
Stevens was delighted to clinch his first Classic win at the age of 50, having retired from racing in late 2005 before making a comeback earlier this year.
"This is the ultimate feeling," said a smiling Stevens, who had also won the $2 million Distaff on Friday, the signature race on the opening day of the 30th Breeders' Cup. "It's actually the culmination of a career.
"I'd been so close so many times and I figured it just wasn't meant to be. I can't believe that it happened. I thought it was going to happen, but I can't believe that it did happen.
"It's sweet to go all these years and not have won it, and then seven years off and come back with a horse like this for these people. It's just so cool, man. It's awesome."
PAYING TRIBUTE
Stevens, who won the Preakness Stakes on board Oxbow in May, paid tribute to Mucho Macho Man's superb performance on Saturday, a year after the horse had finished second in the Classic.
"He was super, super sharp today," he said. "You need a good, clean break, and he left there like a quarter horse today and actually outbroke them. I could have put him on the lead, had him on the lead.
"But he's so push button. He's a big, long striding horse, and he was powerful down the back side. I knew they were coming, but he was super, super tough the last 16th of a mile.
"The race was a mile and a quarter, and not a mile and a quarter and a stride, so it was perfect. Had I known it was that close, I probably wouldn't have celebrated."
With Mucho Macho Man's win, Kathy Ritvo became the first female trainer to win the Classic.
"It feels great. Very, very good," said Ritvo, who has had a heart transplant. "But I'm happier for my horse. He deserves it. When Gary waved the stick, I figured he won. He got a great trip. Gary did a fantastic job."
Will Take Charge, who had won his two previous races, had to settle for second place after coming desperately close to a come-from-behind win over the last few yards.
"It's a heartbreak to lose one like that," said the three-year-old colt's veteran Hall of Fame trainer D. Wayne Lukas.
"He was after him, closed on him. He's really developed into a beautiful horse and he did everything right today.
"Other than the (Kentucky) Derby, this is the one you want. I thought we had a shot to get it today and just came up a jump short."
Hall of Fame trainer Bob Baffert, who has enjoyed success in most of the other top races in the United States, once again came up empty in his bid for a first victory in the Classic.
"When I saw him (Game On Dude) going real fast on the back stretch, I knew I was going to be in trouble," said Baffert whose other horse in the race, Paynter, finished seventh.
"Then when (jockey) Mike (Smith) asked him, there was nothing there. I feel bad I got beat; you always feel bad when you get beat, but I feel worse for the horse.
"My other horse (Paynter) gave it his best."
(Reporting by Mark Lamport-Stokes; Editing by Greg Stutchbury)
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