Wolves striker Bakary Sako's spectacular strike 12 minutes from time ensured Blackburn's first home game of the post Steve Kean era ended in defeat.
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A crowd of 17,034 was comfortably Rovers' highest of the season as hoards of disgruntled fans returned to Ewood Park to mark the end of Kean's deeply unpopular reign.
But they were subjected to a lacklustre performance as caretaker boss Eric Black stuck with the five-man defence that secured a goalless draw at Nottingham Forest in midweek, leaving forwards Jordan Rhodes and Colin Kazim-Richards to probe manfully with little service.
Rhodes had claims for penalties rejected in each half and his strike partner spurned Rovers' best chance shortly after Sako's magnificent long-range effort left goalkeeper Paul Robinson with no chance.
Stale Solbakken's Wolves leapfrog their opponents to go third on the back of three consecutive wins on the road, while Blackburn fall to ninth with no victory in four matches.
Wolves started the brighter of the two sides and Sako drew a fine early save from Robinson, firing a loose ball through a crowd of defenders.
Moments after a robust challenge from Karl Henry on Kazim-Richards went unpunished, Rovers had a penalty appeal waved away by referee Nigel Miller when Rhodes went to ground under the attentions of Richard Stearman.
The visitors should have taken the lead in the 19th minute, Sylvan Ebanks-Blake thudding a header against the post from Kevin Foley's cross.
Kazim-Richards almost found a vital touch at the end of Martin Olsson's teasing left-wing cross before the Blackburn striker was clattered on the knee with half an hour gone - Henry failing to escape a booking on this occasion following a heated altercation.
Rhodes' poachers instincts were on display five minutes before half-time when he collected the scraps from a goalmouth scramble to force a reaction stop from Wolves keeper Carl Ikeme.
The Scotland international striker had another penalty shout turned down early in the second half when he grappled with Roger Johnson and continued to look like Rovers' main threat despite little ammunition.
In the 51st minute Blackburn winger Fabio Nunes mishit a cross that landed on the top of the net with Ikeme scrambling.
Wolves got bodies in the way of speculative efforts from Bradley Orr, Danny Murphy and Kazim-Richards before the visitors regained the attacking impetus they showed in the first half.
Substitute Anthony Forde might have done better when he curled beyond the far post following excellent work from Sako.
In he 78th minute, Sako decided to do the work himself to glorious effect.
Blackburn only partially cleared a corner and the ball fell to the Frenchman, who took a fine first touch to engineer space and rifled a superb 25-yard effort beyond Robinson.
Rovers almost levelled moments later when Nunes produced a delicious cross that caused confusion between Ikeme and Wolves centre-back Christophe Berra, but Kazim-Richards could not direct his close-range header goalwards.
As the hosts belatedly committed men forward, Forde burst forward on the counter attack in stoppage time but blazed wide with only Robinson to beat and fellow substitute Ronald Zubar unmarked.