It took just 30 seconds for Chelsea to spoil Mourinho's comeback as Pedro pounced on a defensive mix-up to score the fastest Premier League goal of the season so far.
Gary Cahill thumped his second goal of the season on 21 minutes, before Eden Hazard deepened Mourinho's misery with a fine 62nd-minute strike.
N'Golo Kante then completed the rout with Chelsea's fourth on 70 minutes as the visitors capitulated.
The victory, which moved Chelsea into the top four and left United in seventh, fittingly marked the 20th anniversary of former Chelsea vice-chairman Matthew Harding's death.
Antonio Conte stuck with the same team which dispatched Leicester last week, while Jesse Lingard replaced Ashley Young in what was United's only change from Monday's draw at Liverpool.
Ten months after his sacking, Chelsea's most-decorated manager received a warm welcome pre-match, but that quickly evaporated as the hosts hit the front before a United player had even touched the ball.
A lofted pass over the top caused hesitation between the United defence and David de Gea, allowing Pedro to capitalise and turn the ball into the unguarded net.
Having been caught cold, United had the chance to level on eight minutes but Zlatan Ibrahimovic could only head Antonio Valencia's cross onto the roof of the Chelsea goal.
Despite this, the hosts remained in firm control as Hazard volleyed wide from a corner after another defensive lapse from the visitors on 14 minutes.
Chelsea soon underlined their superiority, though, Cahill escaping Chris Smalling's clutches to meet a deflected corner before clinically volleying home.
Marcus Rashford had an attempt blocked shortly after but Manchester United remained in trouble. Pedro pinched possession from Daley Blind, before surging to the byline and firing a low cross that De Gea had to block with his legs.
A minute later, Hazard's low cross almost fell for Diego Costa to make it three but somehow Eric Bailly was able to clear.
Thibaut Courtois almost invited United back into the game on 28 minutes, parrying Ander Herrera's shot into the path of Lingard, but atoned to block the rebound.
The visitors were aggrieved David Luiz was shown a yellow card, rather than a red, for a high challenge on Marouane Fellaini, which would force the Belgium international off at half-time.
In the second period, Chelsea sat back and invited United forward with the intent of hitting them on the counter, a ploy which led to their third.
Valencia and half-time substitute Juan Mata, also returning to his former club, failed to mark Hazard and the Belgian was given the space to weave into the area and convert low to De Gea's left.
Three quickly became four, this time Paul Pogba and Smalling were at fault as Kante was given the freedom to roam into the area and beat a hapless De Gea.
Courtois was on hand to deny Ibrahimovic and Rojo from taking his clean sheet in the closes stages as the Blues sealed a third consecutive victory in style.
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