The Irishman's eighth goal of the season, in a game of few chances, could arguably prove his most important as he fired low past David Stockdale from 12 yards after Ahmed Fathi had been caught on the ball by Tongo Doumbia.
Substitute Jay Simpson came closest for Hull when his strike hit a post but Tigers boss Steve Bruce was left to taste defeat on what was his first return to Molineux since being overlooked for the Wolves post 14 months ago.
Despite the patient passing play on offer from both teams at Molineux, with Wolves maintaining their composure in spite of their precarious league position, the first quarter contained no attempts at goal.
Fathi was first try his luck from distance after 25 minutes with a shot which flew comfortably wide. The Tigers were dealt a blow just minutes later when skipper Robert Koren was forced off due to injury, with the Molineux faithful offering little sympathy for the former West Brom man.
The most obvious danger for Wolves was proving to be their own back-line as goalkeeper Dorus De Vries and his defenders attempted to pass their way out of trouble at every opportunity.
Stephen Quinn, however, thought he had opened the scoring in the 36th minute only to see his deflected strike drift the wrong side of a post. And 60 seconds later Wolves enjoyed their first attempt at goal - much to the delight of the South Bank - as Doumbia drilled off target.
The second half started in similar fashion to the first before, out of nowhere, Wanderers broke the deadlock in the 55th minute.
Fathi got robbed of the ball by Doumbia 25 yards from goal, he found Bjorn Sigurdarson who fed Doyle and the Irishman finished low past Stockdale.
Simpson, on for Koren, fluffed a free shot from 12 yards at the other end as Hull threatened an immediate equaliser.
Simpson then came within inches of an equaliser when he smacked a shot against a post before Wolves forward Sigurdarson fired into the side-netting as the game picked up a pace.
Four minutes of injury time did little for the nerves of the home faithful but Wanderers held out for only their second win in eight meetings with Hull, but more importantly three points which boost their chances of avoiding a return to England's third tier for the first time since 1989.