The 44-year-old Canadian will be representing his fellow athletes and lending his time for public appearances, media interviews and in-venue fan activities.
The Skate Canada International will take place in Mississauga, Ontario, between October 27 and 30, at the Hershey Centre.
The event is the second competition in the annual International Skating Union (ISU) Grand Prix of Figure Skating series.
As an athlete Stojko competed at the Skate Canada International eight times.
He secured a medal on each of his appearances, winning five golds and three silvers.
"I am thrilled to be back at Skate Canada International," said Stojko.
"This event holds many memories for me and I’m looking forward to reflecting on my time as a skater, while supporting the competing athletes.
"I know first hand the pressure these skaters are under and I’m happy to be able to advocate for them through my role as athlete ambassador."
Stojko first joined the Skate Canada National Team in 1990 and went on to become one of Canada’s most successful skaters.
He is a three-time world champion, two-time Olympic silver medallist and seven-time Canadian champion.
Stojko was the first to perform a quadruple combination jump in competition, at the 1991 ISU World Figure Skating Championships in Munich, Germany.
He was also the first to do a quadruple-toe/triple-toe loop combination, in the free programme of the 1997 ISU Champions Series Final in Hamilton, Ontario.