Wayne Rooney and Frank Lampard were England's scorers, either side of a fine equaliser from Fred at the start of the second half.
However, there were far more plusses for manager Roy Hodgson than a first victory over Brazil since 1990.
Jack Wilshere was outstanding alongside Steven Gerrard in midfield, and was deservedly named man of the match, Joe Hart saved a penalty and Theo Walcott's pace was a constant threat until he was replaced by Aaron Lennon near the end.
Indeed, but for a few defensive jitters immediately after the restart, England were comfortably the better side.
And for in-form Rooney in particular, hopes are high that following that deeply misguided red card on his last visit to Montenegro, England will get a more productive contribution from their talisman in Podgorica next month, when the Three Lions bid to get a faltering World Cup campaign back on track.
Rooney has netted 10 goals in 10 games for Manchester United and now five in five for England,
Three England managers had waited two-and-a-half years to pair Gerrard with Wilshere.
Yet Fabio Capello, Stuart Pearce and now Hodgson always had it in mind to use them in tandem should they ever both be available at the same time.
It was Hodgson's misfortune that injury should rule Wilshere out of Euro 2012.
It is his fortune the Arsenal man is now fit. On this evidence, fingers and toes need to be crossed Wilshere stays that way for the next year or so.
For this glimpse of the future was a sight to behold.
Fuelled by the knowledge Gerrard's wise old head was around to rectify any wrong moves, Wilshere was superb.
He does not drive forward in the Yaya Toure manner. It is more picking a moment to make a little dart, or slip a pass through static defenders.
And boy does he have an effect.
It was his astute pass that set Danny Welbeck up midway through the first half, only for the Manchester United man to fire wide with his right foot when the acute angle demanded an effort with his left.
And it was Wilshere who sliced Brazil apart with the pass that provided Walcott with the chance Julio Cesar saved, only for Rooney to calmly stroke home the rebound.
Cesar denied Walcott with another fine stop before the end of as promising a half in a friendly as England have had for some time.
That is not to say Brazil were entirely toothless.
They may have slipped to a record low of 18 in the FIFA rankings but they remain capable of causing anyone problems.
Indeed, they should have gone ahead when Wilshere blocked Oscar's cross with his hand in the area but Hart produced a magnificent double save to repel both Ronaldinho's penalty and the rebound before Neymar bundled the ball wide.
It was the first penalty save by an England keeper since 2004, so Hart deserved the luck he got when Neymar slid in at the far post to meet an Oscar cross from the other side which he somehow managed to scoop over from three yards.
It was undeniably good from England - but it took them just two second-half minutes to undo all that positive work.
That Brazil's equaliser should be self-inflicted just made it worse. The look on Hodgson's face said everything about what had unfolded.
From the edge of his own area, Gary Cahill chose to advance forward.
A lack of control led to him losing possession in no-man's land, the ball rolled to Fred on the edge of the area and with virtually his first touch after being introduced as a half-time substitute, the former Lyon man fired into the corner.
More shambolic defending, this time started by Chris Smalling, provided Fred with another chance which he clipped against the bar two minutes later.
Yet England's response was as impressive as their first-half display had been.
Cahill and Walcott were repelled by Cesar before Rooney nipped in to provide Lampard with an opportunity snaffled in sensational manner, taking him onto 27 England goals and once again raising question marks over Chelsea's desire to off-load him.
It was enough to seal a rare win over such glamorous opposition, with Fred coming closest to earning the visitors a draw after good work by Oscar and Lucas.