Couples rolled in birdie putts on the fourth and seventh holes en route to collecting six skins and $175,000 in the opening nine holes of the 24th annual Skins Game.
Stephen Ames and defending champion Fred Funk were shutout over the first nine holes.
After the other three players missed birdie putts from within 30 feet, Daly collected the first skin as he sank a three-foot birdie putt on the first.
'I thought Freddy (Couples) would make his and I'd just tie him, but it's great to get off to a good start,' Daly said.
Couples and Funk halved the following two holes with birdies. Couples birdied the fourth from outside 25 feet to win three skins and $75,000.
'As I said earlier, you need a skin early and I got it,' said Couples, who has played just twice since the PGA Championship while getting treatment for a blood clot in his arm.
Couples made his fourth straight birdie at the fifth, but it was only good enough to halve the hole with Funk. After Ames, Couples and Funk missed birdie putts on the sixth, Daly had a birdie putt to earn two more skins.
However, Funk and his caddie had a trick up their sleeve first. Funk's caddie gave Daly's caddie a different golf ball and Daly put that ball down by his mark and as he lined up the putt, Funk's caddie moved the ball via remote control. After the shenanigans, Daly missed the birdie putt to make the seventh worth three skins and $100,000.
Couples watched as Ames and Daly missed long birdie putts on the seventh. The 1992 Masters winner rolled in a five-footer for birdie. That gave him three more skins and another $100,000 for a total of six skins and $175,000.
'It's been pretty good so far,' said Couples, who is donating part of his winnings to a fund for fallen firefighters. 'I've hit the ball pretty well and had a good time making some money for the firefighters, so this is a good day.'
The final two holes were halved, No. 8 with pars and No. 9 with birdies. That means the 10th hole, which will be the first hole played Sunday, will be worth three skins and $150,000.
From there, Nos. 11 and 12 are worth $50,000, while 13 through 17 are worth $70,000 apiece. The 18th hole will be worth $200,000.