Daley was just off the green in three on the par-5 12th hole and his chip for birdie to prolong the match barely missed. Scott, who is best known for finishing second to Tiger Woods at the 1996 U.S. Amateur Championship, rolled in his putt for his first professional victory and $24,000.
Scott, Daley, Steve Alker of New Zealand, Scott Hend of Australia and Americans Roger Tambellini and Mark Slawter started the playoff on the par-5 18th.
Slawter was the first to go when he failed to make birdie. The 18th was played again and Hend departed when he could do no better than par.
Tambellini was ousted when he could not make a par on the third extra hole - the par-5 12th. It appeared that Scott too would not advance until he drained a 30-foot birdie putt.
The three remaining players then proceeded to the par-3 13th, where Scott and Daley each made par.
Alker, the defending Canadian Tour McDonald's Order of Merit Champion, hit the pin from a greenside sand trap on the 13th but missed the par putt.
Scott and Daley then returned to the 18th and each birdied.
The previous largest playoff on the Canadian Tour occurred at the 1997 TELUS Edmonton Open, which was won by South African Manny Zerman.
The longest playoff in Canadian Tour history took place in 1992, when Lee Chill outlasted current PGA Tour star Chris DiMarco on the 11th hole at the Willows Classic in Saskatoon.
Scott earned his way into the playoff with birdies on the final two holes of regulation for a 5-under 67.
Daley, who was in the final group, also birdied the final hole to reach 12-under.
Alker, the top money winner on the 2000 Canadian Tour, missed winning outright when he left a birdie putt on the edge of the cup on the 72nd hole.
Full-field scores from the TELUS Vancouver Open