Larkin scored on a breakaway off a pass from Gustav Nyquist after the Red Wings gave up three goals in the third period.
"It feels good, 40 minutes we were the better team, we played the way we wanted to come out and play possessing the puck and capitalizing on our chances and moving the puck around," Larkin said. "All four lines were generating and doing a good job against their big guys. It was 20 minutes where we took our foot off the gas and let their best players come in waves. We could feel it when that happened."
[WATCH: All Red Wings vs. Maple Leafs highlights]
Video: EA Sports Overtime Winner: Larkin wins it for Detroit
Nylander had no points playing 12:48 for the Maple Leafs (20-8-1). The restricted free agent forward agreed to a six-year contract Saturday and had not practiced with his teammates.
"It felt OK. There's a lot of difference from practicing by yourself and with the team back home (in Sweden)," Nylander said. "Started feeling better and the legs were OK, so it felt like an OK first game."
Video: DET@TOR: Glendening bangs home shot from the slot
Larkin, Nyquist and Mike Green each had a goal and an assist, and Jonathan Bernier made 27 saves for the Red Wings (13-12-4), who have scored at least four goals in five of their past six games.
"The thing I said to our guys in the end was that in the end we were better than them for two periods," Detroit coach Jeff Blashill said. "Sure they were better than us in the third, but let's not take away from the fact that for two periods we were the better team, and I thought in overtime we were the better team. They pushed hard. Would you like to salt that game away and win 4-1? Of course you would. But that's not how it goes all the time."
Kasperi Kapanen and Andreas Johnsson each had a goal and an assist, and Garret Sparks made 27 saves for the Maple Leafs, who had won five in a row.
Video: DET@TOR: Green scores through traffic to pad lead
"Even though we got the first goal, we just didn't control the play enough or generate enough momentum," center John Tavares said. "They made it frustrating blocking a lot of shots and just didn't give us a whole lot. We got some life in the third and it was good to get a point."
Tavares got Toronto within 4-2 at 2:38 of the third period when he took a pass from Morgan Rielly in the slot, Zach Hyman made it 4-3 at 8:50 after getting a pass at the top of the goal crease from Igor Ozhiganov at the blue line, and Johnsson tied it 4-4 at 11:36 when he got a rebound off the end boards from an Auston Matthews shot.
"Even though we made a few mistakes in the third when they came out hard, I thought we didn't panic going into the OT," Bernier said. "I thought it was all us, and that proves a lot."
The Maple Leafs took a 1-0 lead at 4:50 of the first period when Kapanen took a cross-crease pass from Jake Gardiner.
Jonathan Ericsson tied it 1-1 at 5:23 with a slap shot from the blue line, and Luke Glendening put Detroit up 2-1 at 6:28 off a pass from Niklas Kronwall in the slot.
Video: DET@TOR: Tavares buries wrister from the circle
"Those are huge goals, momentum is a big thing in this league, especially on the road, especially in this building and against that team," Blashill said. "All of a sudden we quelled momentum and now it just becomes a hockey game."
The Red Wings made it 3-1 with 14 seconds left in the period when Nyquist took a pass from Larkin and shot from the left face-off dot.
Green made it 4-1 at 11:07 of the second period with a slap shot from the blue line.
"We did a lot amongst ourselves as far as talking about not letting a 4-1 lead going into the third period for the other team deter us from trying to win that game," Sparks said. "We were able to battle back and get a point, and that's all kudos to the guys in front of me. What happens from there, it's just I've got to make another save."
Video: DET@TOR: Fans give Humboldt Broncos standing ovation
They said it
"Obviously it's not our game plan to lose a three-goal lead in the third, but I think it was strong by our team to come back in OT even though we gave up a three-goal lead. We knew going into the game they have a lot of firepower on that team. If we play like we did in the first two periods, we're a good team." -- Red Wings forward Gustav Nyquist
"I thought Willy (Nylander) was fine. It was probably unfair for me ... we were supposed to practice together, we never even gave the guy a practice. We wanted to get him in. You've got two guys on that line, one coming back from injury (Auston Matthews) and one who hasn't played. In the end, we had an opportunity, we felt, to get going. We tried to get going. It has nothing to do with Willy, it has to do with me and trying to win the game, that's all." -- Maple Leafs coach Mike Babcock on William Nylander, who played 2:07 in the third period and did not play in the overtime
Need to know
It was Larkin's third overtime goal, tying him with Herbie Lewis (1933-34), Steve Yzerman (2000-01) and Brendan Shanahan (2003-04) for most in a season in Red Wings history. ... Kronwall played his 900th NHL game, all for Detroit. .. Mitchell Marner had an assist to become the third Maple Leafs player in the NHL expansion era (since 1967-68) to reach 40 points in 30 games or fewer (Doug Gilmour, 28 games in 1992-93 and 30 games in 1993-94; Darryl Sittler, 28 games in 1977-78 and 29 games in 1976-77). Marner has six goals and 34 assists, and a six-game point streak (12 assists).
Red Wings: Host the New York Islanders on Saturday (7 p.m. ET; FS-D, MSG+, NHL.TV)
Maple Leafs: At the Boston Bruins on Saturday (7 p.m. ET; NHLN, CBC, SN, SN1, NESN, NHL.TV)
Video: Red Wings withstand comeback attempt, win in OT