The pre-season showpiece brings together the Premier League champions with the FA Cup winners, but after Chelsea had achieved a domestic league and cup double under Carlo Ancelotti in the previous season, United were included after finishing as runners-up in the league.
It was a re-run of the 2009 final, where after the two sides played out an entertaining 2-2 draw, Chelsea emerged victorious by a 4-1 scoreline in a penalty shootout.
That had been the fourth occasion that the Blues had won the shield, while United were bidding to win the fixture for a record 18th time this time around.
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The opening exchanges were fiercely contested, but despite United looking threatening in attack, it was Chelsea who drew several saves out of goalkeeper Edwin van der Sar.
But it was the Old Trafford outfit who took the lead through the impressive Antonio Valencia, who latched onto Wayne Rooney's pass just before half time to dispatch the ball past the helpless Henrique Hilario.
That put Sir Alex Ferguson's side into the ascendancy, but Chelsea continued to pepper the United goal, drawing more stops out of the reliable Van der Sar.
However, like in the first half, Manchester United struck to effectively seal the trophy when Hernandez came off the bench to net a debut goal in fortuitous circumstances, with the ball deflecting off his face and into the net.
That goal failed to deter Chelsea, and they had real momentum after Salomon Kalou converted a close-range opportunity with seven minutes remaining.
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That brought an end to what had been an enthralling encounter ahead of the new season, and one that set up both teams to go toe-to-toe for the Premier League title.
Manchester United made an indifferent start to the year, but once they developed a rhythm they were very difficult to stop.
Chelsea endured contrasting fortunes, making a blistering start to the campaign before a disappointing winter ensured that they were playing catch-up for the remainder of the season.
The Blues won eight games from nine from the middle of February, but with United not looking like faltering, they saw the Red Devils wrap up a nine-point victory to win a record 19th league title.