Mick McCarthy's in-form side tasted defeat at their Midlands rivals when Elliott Ward grabbed the winner in the 71st minute.
Coventry dominated from the start and should have been awarded a penalty in the fourth minute when Michael Mifsud appeared to be tripped inside the box by Gary Breen, but referee Peter Walton waived away the home team's appeals.
Wolves were clearly beginning to feel the pressure as Michael Kightly and Jackie McNamara were booked for late challenges.
It was no surprise when the home team grabbed the lead in the 26th minute.
Stephen Hughes' free-kick bounced inside the area before Dele Adebola knocked the ball in from close range.
The visitors were reduced to ten men in the 45th minute when the referee showed a second yellow card to McNamara after he dragged down Isaac Osbourne.
The home fans were stunned when Wolves equalised in injury-time with their first shot on target.
Andy Marshall pulled off a diving save to deny Seyi Olofinjana's header, but the rebound was slammed into the net by Kightly.
The Sky Blues were determined not to let Wolves off the hook after the break and Matt Murray needed to be alert to tip Mifsud's 20-yard shot around the post after he had latched on to Adam Virgo's pass.
Coventry made their possession and their extra man count to retake the lead when a corner from Hughes on the right fell to Ward on the edge of the six-yard box and he slammed home his third goal of the season.