Nani and Ashley Young failed to convert United’s two penalties as the sides needed a three-penalty shootout to decide a match that Barcelona had dominated.
But it could have been different for United had Victor Valdes not denied Wayne Rooney from the spot in first half stoppage time – with Rooney slashing the rebound wide.
Manchester United had the better of their friendly against Barcelona at FedEx Field in Washington DC this time last year, with Michael Owen scoring the winner on that occasion.
But despite Paul Scholes looking in inspired form Barcelona dominated from early on this time around, and the Catalan giants should have led when Lionel Messi drove at the United defence before feeding Cristian Tello, who took too long to shoot – and could only find the side-netting.
Barca came even closer moments later when Messi jinked his way beyond Antonio Valencia and drilled a low shot towards the bottom corner, but David De Gea pulled off a superb fingertip save low to his left - the first of many excellent saves by the former Atletico Madrid keeper.
Barca opened United up at will and they spurned another big chance when Messi again found Tello in space on the left, but Rio Ferdinand made up enough ground to deflect the shot over the bar.
The game’s big moment came in first half injury time when Tello clumsily brought down Nani in the box, but Rooney’s powerful penalty was at a comfortable height for Valdes to palm away.
Rooney was first to the rebound, but snatched at it and the ball flew wide.
Andres Iniesta, Messi and Rooney were among the big names rested for the second half, but United’s new signing Shinji Kagawa came off the bench and almost made an instant impact.
Collecting Danny Welbeck’s cushioned pass, Kagawa tried to coax the ball into the bottom corner – but Jose Manuel Pinto, another player introduced at the break, made an accomplished save low to his right.
But it was mostly one-way traffic in the second half as Barca threatened to get their noses in front, but they were unable to breach De Gea, who was in inspired form.
The Spaniard, playing his first game for United this summer having represented Spain at the European Championships and the London Olympics, made two crucial saves – one with his legs from Alexis Sanchez, and the second an acrobatic flying save from Pedro’s goalbound header.
Chances came and went as the game limped towards an inevitable conclusion, with Xavi and Pique each scoring from the spot to ensure victory for the Catalan club.