Ollie Watkins scored a second-half winner to condemn 10-man Chelsea to a narrow 1-0 defeat at Stamford Bridge.
Both teams had opportunities to take the lead in an intriguing first period, with Chelsea stopper Robert Sanchez forced to make two crucial saves from Lucas Digne and Nicolo Zaniolo, while the hosts saw a goal ruled out for an offside infringement.
Chelsea started the second period on the front foot, but the tide turned in the 58th minute when Malo Gusto was shown a straight red card for a studs-up tackle on Digne.
Matters got worse for the hosts when Watkins put the visitors in front with his first Premier League goal of the season.
The visitors saw out the remainder of the contest to bounce back from Thursday's Europa Conference League defeat with a second straight Premier League victory.
While Aston Villa move up to sixth place, Mauricio Pochettino's side are left in 14th position with just five points to their name after six matches.
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Chelsea controlled possession in the opening stages of the contest, but they failed to convert their early dominance into clear-cut chances.
Instead, it was the visitors who went close to taking the lead in the 19th minute when Digne produced a fierce volley which forced Sanchez to tip the ball over his crossbar.
Digne's effort seemingly brought the contest to life, as Chelsea carved out an opportunity of their own just minutes later.
Mykhaylo Mudryk picked out the run of Nicolas Jackson with a superbly-weighted reverse pass, but the Senegal international was denied by the onrushing Emiliano Martinez.
As the contest approached half time, Sanchez was called back into action following a well-worked set-piece routine from the visitors.
A corner was stood up to the far post where Boubacar Kamara was waiting to head the ball back into the path of Zaniolo, whose powerful volley drew another fine stop from Sanchez.
There was still time in the first period for summer signing Axel Disasi to nod the ball into the net, but his headed effort was swiftly chalked off for offside.
With the contest still goalless at the break, Raheem Sterling led Chelsea's search for an opener in the early stages of the second period.
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The England international lost out to Martinez in two promising one-on-one opportunities, although the second strike would have been a tight offside call if he had found the net.
Chelsea's momentum was halted moments before the hour mark when Gusto was given his marching orders for a dangerous challenge on Digne following a VAR review.
Unai Emery's side made full use of the numerical advantage, taking the lead through Watkins in the 73rd minute after Moussa Diaby pounced on a mistake from Thiago Silva in the Villa half.
Having been released by Diaby, Watkins drove into the box and drilled the ball into the bottom corner after his initial effort was blocked by Levi Colwill.
Ben Chilwell nearly found an instant equaliser, but Martinez reacted well to dive down low to his right, ensuring that Villa's lead remained intact.
Jacob Ramsey then went close to adding a second for the visitors, with a curling shot that was finely saved by Sanchez at full stretch.
As it proved, Aston Villa did not require the cushion of a second goal, as they held firm to pile the pressure on Chelsea, who are now winless in three games.
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