The Toffees could not have wished for a better start as Dwight McNeil opened the scoring in the 16th minute before Dominic Calvert-Lewin doubled the visitors' advantage.
However, Everton were more aware than most teams about how precarious a two-goal lead can be after they conceded three late goals to lose 3-2 against Bournemouth before the international break.
Unfortunately for the Everton faithful, they left Villa Park with a sense of Deja vu as the hosts showed great character to turn the game on its head.
Ollie Watkins netted his first Premier League goal since April to give Unai Emery's side a foothold before the half-time interval.
The England international went on to grab his and Villa's second in the 58th minute, pouncing on Jack Harrison's error to pull the side on level terms.
Watkins's brace ultimately proved to be the appetiser for Jhon Duran to the game's iconic moment, unleashing an unstoppable long-range shot into the top corner to clinch all three points for the Villans.
The win ensures Villa will finish the day in third position, while Everton are languishing at the foot of the table without a point to their name after four matches.
ASTON VILLA VS. EVERTON HIGHLIGHTS
McNeil goal vs. Aston Villa (16th min, Aston Villa 0-1 Everton)
Everton take the lead against the run of play. McNeil steals possession from his former teammate Amadou Onana, before driving towards the edge of the box and firing a low strike into the bottom corner to spark scenes of jubilation among the travelling support.
Calvert-Lewin goal vs. Aston Villa (27th min, Aston Villa 0-2 Everton)
Everton double their advantage before the half-hour mark. After netting the opener, a confident McNeil whips an inswinging free-kick into the danger zone for Calvert-Lewin to direct a downward header past Emiliano Martinez. The goal stands following a VAR check for a potential offside.
Watkins vs. Everton (36th min, Aston Villa 1-2 Everton)
Villa establish a crucial foothold courtesy of Watkins. The England international towers over Michael Keane at the far post to head the ball in from Lucas Digne's lofted cross.
Watkins goal vs. Everton (58th min, Aston Villa 2-2 Everton)
Villa pull themselves level before the hour mark. In his attempt to intercept a pass, Harrison can only divert the ball into the path of Watkins, who requires no invitation to fire a first-time finish past the helpless Pickford.
Duran goal vs. Aston Villa (77th min, Aston Villa 3-2 Everton)
What a strike! What a way to win the contest! Substitute Duran produces a spectacular long-range effort to clinch all three points. The unstoppable strike bends out of the reach of the outstretched Pickford and finds a home in the top corner.
MAN OF THE MATCH - OLLIE WATKINS
While Duran produced the game's magical moment, Watkins was undoubtedly the standout performer in the five-goal thriller at Villa Park.
Watkins was back to his clinical best as he ended his Premier League goal drought with a brace, scoring with his head and right foot to demonstrate his qualities as Villa's main striker.
The 28-year-old may have only had 19 touches in the contest, but his brace ultimately changed the course of the game and laid the foundation for Duran to net the winner.
ASTON VILLA VS. EVERTON MATCH STATS
Possession: Aston Villa 73%-26% Everton
Shots: Aston Villa 8-2 Everton
Shots on target: Aston Villa 6-3 Everton
Corners: Aston Villa 6-2 Everton
Fouls: Aston Villa 10-12 Everton
BEST STATS
WHAT NEXT?
After pulling off a comeback victory, Aston Villa will now turn their focus to their anticipated Champions League opener against Young Boys.
As for Everton, they will be desperate to claim a win in their midweek EFL Cup meeting with Southampton at Goodison Park.