The rookie deked, drew the puck to his backhand and put it past Hasek and into the back of the net to score the only goal in the shootout as the Blackhawks rallied past the Wings 4-3 in their United Center season debut.
The Hawks (1-1) rallied from a two-goal deficit on James Wisniewski's short-handed goal early in the third period, and former Red Wing Robert Lang's game-tying wrist shot with 3 minutes 40 seconds remaining to set up Kane's heroics.
"He was better than me today," Hasek said of Kane. "He made a nice move to the backhand. I closed my 5-hole and he made the move before I put my pad down and my glove and he scored the goal. It's a good move. Next time maybe I do something different."
Nikolai Khabibulin stopped all three Red Wings shots in the shootout to record the victory and give the Hawks their first victory of the season after suffering a tough 1-0 loss Thursday night in Minnesota.
"It has been quite a whirlwind the past couple of months," Kane said. "First you're playing in the OHL and then getting drafted in the NHL, and then the next thing you know you're in the NHL going down [ice] on Dominik Hasek. It's a great night for me.
"I was just thinking about getting the move down and making sure I sold the fake pretty good and trying to give the fans something to cheer about."
There wasn't much to cheer about early as the Red Wings took a 2-0 lead early in the second period on goals from Brian Rafalski and Nicklas Lidstrom.
The Hawks scored their first goal of the season when Kane made a nice cross-ice pass to Magnus Johansson, who then fed Tuomo Ruttu who put it past Hasek.
Detroit added a goal in the third when Tomas Holmstrom tipped in a Rafalski shot for the Wings' second power-play goal. The Hawks cut the lead to 3-2 when Wisniewski and Kevyn Adams broke in on Hasek two-on-one short-handed, and Wisniewski buried a feed from Adams.
Lang, who joined the Hawks as a free agent after playing the last two seasons in Detroit, tied it 3-3 with a wrist shot over the glove former teammate Hasek.
"That one was for Mr. Wirtz," Hawks coach Denis Savard said referring to the death of team owner Bill Wirtz on Sept. 26. "Great win. We just stuck with what our game plan was and the character of our guys showed. They never quit."