The Villa winger rounded off a fine victory for Stuart Pearce's men with a second half strike after substitute Frazier Campbell had put them ahead.
The introduction of Arsenal whizkid Theo Walcott on 62 minutes was a clear turning point as England took the lead five minutes later and the young Gun then set up Milner for the second on 73.
Villa star Milner lined up alongside club teammate Gabriel Agbonlahor but the striker will have been disappointed with the level of his performance.
Agbonlahor is thought to be struggling with an injury and surely it is now time to give him a break.
Penalties
Milner is far from tired, though, and after being brought down in the box with just half an hour gone, the Villa man got to his feet in order to take the spot-kick.
Unfortunately, Spain's highly rated stopper Sergio Asenjo was equal to the low strike and the scores remained level.
Villa players have a history of missing penalties in high-profile tournaments, with Gareth Southgate, Darius Vassell and Olof Mellberg all costing their countries dear during the last decade or so.
But, Milner was not prepared to let it get him down and his fine display was rewarded with the goal which sealed the win.
The former Leeds man was then booked on 82 to complete an eventful but enjoyable evening.