Pictures and report of Rotherham 1 Wolves 0
Substitute Ryan Hall struck to stun Wolves and condemn Kenny Jackett's men to defeat at Rotherham United.
Hall fired in after goalkeeper Carl Ikeme denied Craig Morgan with just 14 minutes left.
Similar to Tuesday's night's League Cup defeat to Northampton, Wolves dominated possession but could not find the killer touch.
Bakary Sako was twice thwarted by goalkeeper Adam Collin and Rajiv van La Parra had a shot cleared off the line in the first half.
They could not break the hosts' impressive defensive rear-guard in the second half, with Sako firing wide and Matt Doherty shooting over.
Jackett reverted back to the side who beat Norwich 1-0 on the opening day of the season with Nouha Dicko recalled against his former loan club.
Rotherham handed debuts to Chelsea loanee John Swift and Paul Taylor, who joined on loan from Ipswich this week.
The hosts, in their first Championship game at the New York Stadium, started brightly and wanted a penalty inside the opening two minutes when the ball struck Danny Batth's shoulder.
Wolves began to take control through and should have gone ahead on 14 minutes after Adam Collin's rush of blood.
He failed to gather Craig Morgan's chest back but recovered brilliantly to produce a superb double save to deny Sako.
It was a warning for Rotherham but they responded with a golden chance of their own seven minutes later when Taylor turned Richard Stearman only to hit the bar from 10-yards.
It was the only worry for Wolves in the first half though as they maintained an degree of control and should have gone into the break 1-0 up.
Collin continued to be his own worst enemy and got lucky on 33 minutes when his clearance was charged down by Sako.
The keeper managed to deny the striker only for the ball to run to van La Parra, whose effort was cleared off the line by Kari Arnason.
The Millers frustrated Wolves but Dicko almost gave them a first-half lead on 42 minutes when he turned past Broadfoot, only for his clever chip to drop just wide.
The second half continued the theme of Rotherham holding back Jackett's men, with success.
Sako fired two free kicks wide and Matt Doherty's strike was deflected over by Arnason after another gaffe from Collin.
But, against the run of play, Rotherham won it with 14 minutes left when Ikeme parried Morgan's header and substitute Hall fired in the rebound.