Phoenix took a two-goal lead on Vrbata's team-leading 23rd goal 1:30 into the third period, but Ottawa's Chris Neil responded with his ninth just 16 seconds later.
Mike Smith kept the Senators from scoring again, making 12 of his 32 saves in the final period to help Phoenix end a three-game losing streak. Shane Doan and Gilbert Brule also scored for the Coyotes.
Daniel Alfredsson scored his 17th goal in the second period, but had another waved off due to a goalie-interference penalty on Nick Foligno. The Senators head into Sunday's NHL all-star game in Ottawa on a three-game losing streak.
Ottawa had been on a roll, earning at least a point in a club-record 11 straight road games, before losing to Anaheim and then Los Angeles on Monday.
While the Senators were looking to get back on track before hosting the all-star game, forward Kyle Turris was hoping for a little payback against his former team.
The third overall pick of the 2007 NHL draft went through contentious negotiations with the Coyotes that lasted into the season before finally signing a two-year, US$2.6-million deal on Nov. 22. Turris had no points in six games after signing the contract and was dealt to Ottawa on Dec. 17 for young defenceman David Rundblad.
Phoenix fans — the few thousand who showed up — greeted Turris with boos every time he touched the puck and Adrian Aucoin, back after missing four games with a lower-body injury, dropped his former teammate to the ice with a shoulder on his opening shift, setting off a small scrum.
Turris had one good scoring chance stuffed by Smith in the second period for his only shot on goal.
The Coyotes had a lot more to worry about than their former teammate, though.
Going through a difficult stretch in the schedule and a string of injuries, Phoenix had lost six of seven, including two straight to open a six-game homestand that spans the all-star break.
The Coyotes tried to push the pace against the tired Senators, creating some good chances, and Ottawa fought back with some good ones of its own later in the period.
Phoenix ended the first with the lead, thanks to Brule's third goal of the season, a one-timer near the left post after Mikkel Boedker held the puck at the right post and circled in front.
The second period was a lot like the first: Phoenix pressured early, Ottawa responded, Coyotes get a goal late. Doan scored it, gathering in a rebound of Lauri Korpikoski's shot with his skate before punching it in at the left post for his 15th of the season.
This time, Ottawa had an answer, scoring 91 seconds later on Alfredsson's one-timer on a nice feed from behind the net by Foligno.
Notes: Phoenix C Daymond Langkow returned after missing the previous game with an upper-body injury. ... Ottawa killed off three penalties and has allowed one goal in 29 power-play chances in nine games. ... Korpikoski played his 200th NHL game.