In a game that had Manchester City connections aplenty, the Lionesses came from a goal behind to level late on and then grab victory in extra time.
With no less that 13 players in this clash either playing for City or former City players, it was a proud night for the club.
Keira Walsh, Lauren Hemp and Ellen White all started for England, while Ellie Roebuck, Alex Greenwood, Demi Stokes, and Chloe Kelly began on the bench.
Leila Ouahabi and Laia Aleixandri both started on the bench for Spain.
In a first-half largely dominated by Spain, Ellen White had a couple of opportunities to open the scoring, flicking a Beth Mead cross wide and then seeing a goal ruled out for offside following a VAR check.
But it was La Roja who went into the break the happier of the two teams, with the Lionesses second best in most departments.
Though England began the second period brightly, it was Spain who broke the deadlock nine minutes after the restart.
Sub Athenea del Castillo beat Rachel Daly to the ball on the right of the box before teeing up Esther Gonzalez who had time to control the ball and then tuck it into the bottom left corner.
White was replaced by City team-mate Kelly shortly after in a bid to freshen the attack up and Hemp appeared to be fouled in the box on the hour-mark but the referee waved penalty appeals away.
Aleixandri was introduced on 71 minutes as Spain looked to see out the time that remained and Greenwood came on for England on 82.
Then, finally, the Lionesses levelled with just five minutes remaining.
Hemp’s deep cross found the head of Alessio Russo who nodded the ball down for Ella Toone to volley home from close range to send the packed AmEx Stadium wild.
It was enough to force an additional 30 minutes, much to the delight of the 28,994 crowd.
Just two minutes into extra time, Walsh played an exquisite threaded pass to Hemp in the Spain box, but the ensuing cross was blocked and the danger cleared.
Four minutes after that, Walsh fed former City favourite Georgia Stanway was allowed time and space to drill a stunning 20-yarder past the keeper to put England 2-1 up.
Walsh limped off on 116 minutes and Hemp’s night also ended, with both being replaced by former team-mates Jill Scott and Nikita Parris.
England comfortably saw the minutes that remained out to book a place in the last four and edge closer to winning a major trophy for the first time.