Daicos collected 41 disposals and the 38-year-old Pendlebury had a hand in five goals in the Magpies' 11.12 (78) to 9.12 (66) victory on Sunday night.
The Pies, with halfback Dan Houston (28 touches) superb and Jordan De Goey kicking three goals, won before a crowd of 82,528 at the MCG - the largest home-and-away attendance in St Kilda's history.
Acting captain Nick Daicos, his brother Josh (36 disposals) and Pendlebury - who amassed 26 disposals in just 55 per cent of game-time - were brilliant.
Pie Harry Perryman curtailed the output of Saints ace Nasiah Wanganeen-Milera, who kicked a goal and had 19 touches, while Beau McCreery and Lachie Schulz scored two majors apiece for the winners.
"It was really nice to wake up our muscle memory, that our system works," Collingwood coach Craig McRae said.
St Kilda's prized signing Tom De Koning (20 disposals, 16 hit outs) was busy, as was fellow recruit Sam Flanders (28 possessions), while other newcomers Liam Ryan (one goal) and Jack Silvagni (19 touches) turned in serviceable efforts.
The Saints' chief ball-winners were Jack Sinclair (35 touches) and Marcus Windhager (29) while Cooper Sharman and Mitch Owens kicked two goals each.Â
The Saints started brightly, scoring the initial two goals before the Pies responded in style with the next four, with Nick Daicos and Pendlebury the architects.
After Jordan De Goey snapped the Magpies' first major, handballs from Nick Daicos and Pendlebury set him up for another.
Pendlebury had a hand in Collingwood's next two goals, with shrewd handballs helping Lachie Schulz and Dan McStay to score.
The Pies led 4.3 to 2.4 at quarter-time but the Saints rallied with three consecutive goals in the second term. When Sharman slotted his second, they led by nine points.
But a late strike from Collingwood's Schulz after a pinpoint left-footer from Steele Sidebottom reduced the margin, with the Saints up 5.7 to 5.5 at halftime.
Pendlebury again revelled early in the third quarter with the 426-gamer twice setting up goals to Beau McCreery, the first with an overhead handball, then a hand-off when lining up from 50 metres.
The Pendlebury-McCreery double act came as the Magpies seized control with five goals to two to turn their slender half-time deficit into an 18-point lead at three quarter-time, 10.10 to 7.10.
St Kilda drew within six points after the opening two goals of the final quarter, before Magpie veteran Jamie Elliott converted after a strong mark to give the Pies precious breathing space.
"Clearly, either connection, contest, cleanness, or taking full opportunities or three-quarter opportunities and hurting them, wasn't at the level required," St Kilda coach Ross Lyon said.
"They executed more of their opportunities."
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