Although they scored with two of only three efforts they managed on target, Wolves had attacked with real pace and looked the dominant side before the break.
They finally they got the goal their fans were craving when summer signing Kieran Trippier neatly weighted a pass inside from the right flank, Fer Lopez spun his marker to deliver a lovely pass down the inside-left channel and Munetsi ran through to finish left-footed past Rovers keeper Balazs Toth.
But Rovers quickly levelled when, from a corner, the visitors retained possession and Ryoya Morishita curled over a right-wing near-post cross and McLoughlin deftly glanced his header across home keeper Dan Bentley and into the bottom corner.
Twice Rovers survived when Lopez and Mateus Mane both caught the home backline flatfooted only to fire wickedly dipping shots just over the bar.
But Wolves were made to pay when Gudjohnsen - son of former Bolton Wanderers and Chelsea striker Eidur Gudjohnsen - netted from close range at the near post following Dapo Afolayan's burst down the right.
The mood changed as Wolves failed to find the spark they were looking for despite the introduction of Jimenez - and it looked like former West Bromwich Albion boss Mowbray's men would see it out.
But Jackson Tchatchoua's cross struck the outstretched right arm of the hapless Alebiosu on the edge of the penalty area, referee Hallam was in no doubt - and Jimenez did the rest.
He and his wife had marked his league return to Molineux by kitting out 5,000 fans with black scarves saying 'SI SENOR' to acknowledge his old terrace song - and they were raised in union as he slotted home the spot-kick.