Frank Lampard celebrated claiming the England captain's armband by scoring the goal that secured victory against World Cup holders Spain at Wembley.
Lampard - leading his country in the absence of rested Chelsea team-mate John Terry - headed in from close range in the 49th minute after Darren Bent had struck the woodwork.
The world and European champions dominated possession and territory for long periods and almost equalised late on when David Villa struck a post and substitute Cesc Fabregas wasted a chance.
But England held on with real resilience for a win that will inject new reserves of confidence into Fabio Capello's side.
Capello was missing his son's wedding in Milan to take charge - yet his reshaped England team gave him cause for a double celebration as they overturned the odds in front of a delighted Wembley gallery.
England's win was built on industry and discipline, epitomised by the performances of Manchester City's Joleon Lescott in defence and Scott Parker in midfield.
Lescott gave his finest England performance alongside his former Everton team-mate Phil Jagielka, who also excelled despite playing with a fractured toe, while Parker was given a deserved standing ovation when he was substituted late on.
And Capello will also have drawn satisfaction from lively substitute performances by debutant Jack Rodwell and Manchester United striker Danny Welbeck.
Spain failed to move through the gears despite exerting control for lengthy spells and a measure of perspective must be applied immediately to the outcome.
England will not be catapulted among the favourites for Euro 2012 as a result of this win, but no victory against Spain is earned easily and it is right they take great heart from their efforts as they now prepare to play Sweden at Wembley on Tuesday.
Capello was keen to use Phil Jones, normally a defender, in central midfield - but it was hard work for the Manchester United teenager and his England colleagues in the first half as Spain predictably dominated possession.
England's attacking impetus was limited to one shot from Lampard that was comfortably collected by keeper Iker Casillas, but for all Spain's domination of the ball his England counterpart Joe Hart was unemployed.
Spain made three substitutions at the interval, sending on former Arsenal captain Fabregas, Chelsea's Juan Mata and Liverpool keeper Pepe Reina for Xavi, David Silva and Casillas.
And to the surprise of almost everyone inside Wembley, Reina's first task was to pick the ball out of the net as Lampard headed England into the lead four minutes after the interval.
James Milner's angled free-kick was headed on to the post by the tireless Bent and Lampard the opportunist was perfectly placed to stoop and head in from virtually on the goal-line.
Spain were provoked into a response and Villa almost provided a swift equaliser when he rounded Hart but found the angle too acute and could only hit the side-netting.
Capello then made two changes of his own, sending on Everton's Rodwell for his debut in place of Jones while Lampard was replaced by Gareth Barry.
Rodwell made a good early impression and almost forced Jordi Alba into an error after a breakdown of communications with Reina, but England were unable to take advantage.
Villa was the Spain danger man and he almost put the world champions on terms with 18 minutes left. The Barcelona striker collected Glen Johnson's poor clearance and sent in a dipping volley that beat the diving Hart but bounced back off the post.
As England protected what they had, Fabregas twice came close to marking his return to the country where he played with such distinction with a goal.
Hart saved a deflected shot from the edge of the area then Fabregas turned arguably Spain's best chance wastefully wide from 10 yards after being set up by Villa.
It was England's last anxious moment and the Spanish artists were condemned to a rare defeat.
England: Hart, Glen Johnson, Lescott, Jagielka, Cole, Walcott (Downing 46), Jones (Rodwell 56), Parker (Walker 85), Milner (Adam Johnson 76), Lampard (Barry 56), Bent (Welbeck 63). Subs Not Used: Carson, Baines, Cahill, Terry, Zamora, Sturridge, Stockdale.
Goals: Lampard 49.
Spain: Casillas (Reina 46), Arbeloa, Pique, Sergio Ramos (Puyol 74), Jordi Alba, Busquets (Torres 64), Alonso, Xavi (Fabregas 46), Iniesta (Santi Cazorla 74), Silva (Mata 46), Villa. Subs Not Used: Valdes, Albiol, Monreal, Llorente, Jesus Navas.
Booked: Sergio Ramos, Fabregas.
Ref: Frank De Bleeckere (Belgium).