England captain Harry Kane was fit to play for Bayern Munich and almost equalised at the death, but he could not prevent a first defeat in 43 non-knockout matches in the Champions League.
Unai Emery was also the manager last time they lost – a 3-0 defeat to Paris St Germain in 2017.
Victory underlines what a remarkable job the Spaniard has done since arriving in the midlands almost two years ago, transforming them from relegation candidates to a team who can go toe-to-toe with the best clubs in Europe.
The atmosphere was electric before kick-off with Villa fans basking in their biggest game in over 40 years before falling silent to take in the Champions League anthem for the first time on home soil.
It took a while for Villa to get into it, with Ollie Watkins heading over in the 18th minute as the noise ramped up.
The decibels went through the roof as they thought they had taken the lead in the 23rd minute when Pau Torres poked in a loose ball from a free-kick.
However, mad scenes of celebration were cut short when Jacob Ramsey was ruled offside by VAR from the initial set-piece.
It was a hot spell for the hosts and they came close several moments later as the ball fell to Amadou Onana on the edge of the area but he shot straight at goalkeeper Manuel Neuer.
Bayern weathered the storm and Emiliano Martinez was forced into his first meaningful save, superbly tipping over Michael Olise’s curling effort over the crossbar.
Bayern took control in the second half and began to knock on the door more regularly, with Olise having two shots blocked and half-time substitute Jamal Musiala also denied after dancing into the area.
Villa’s biggest threat came by using their pace on the break and that is how Duran’s winner came about 11 minutes from time.
Torres’ long ball found Duran and, with Neuer woefully out of position, the Colombian shot into an empty net.
There were some nervy moments as Villa defended for their lives and Martinez produced two brilliant saves to win it.
First, he denied Serge Gnabry from close range after the former Arsenal man was played in and then made a sprawling save to claw away Kane’s header at the death.
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