The 22-year-old defender is a surprise inclusion to play in the heart of the visiting side's back four, with Lionel Messi also starting after being cleared fit to play.
With Carles Puyol and Javier Mascherano ruled out through injury, coach Tito Vilanova has shown supreme confidence in the 22-year-old by choosing him to partner Gerard Pique at the back ahead of Alex Song and Eric Abidal.
Lionel Messi also takes his expected place as the spearhead of the Barca attack after the club declared him fit to play earlier on Tuesday, with Pedro and Alexis Sanchez flanking the Argentine in the front three.
Elsewhere, it is an expected lineup from the Catalans, with Victor Valdes in goal, Xavi, Andres Iniesta and Sergio Busquets making up the midfield trio, and Dani Alves and Jordi Alba assuming both fullback spots.
Meanwhile, captain Philipp Lahm, Bastian Schweinsteiger and Javi Martinez all return to Bayern Munich’s XI after being rested for Saturday's 6-1 win over Hannover.
With Mario Mandzukic suspended, Mario Gomez lines up as the lone center forward for the home side, with Arjen Robben, Thomas Muller and Franck Ribery playing as an attacking midfield trident behind.
Coach Jupp Heynckes’ back four is as anticipated, with David Alaba, Jerome Boateng and Dante joining Lahm in defense, while Manuel Neuer get the nod in goal.
Bayern Munich (4-2-3-1): Neuer; Lahm, Boateng, Dante, Alaba; Martinez, Schweinsteiger; Robben, Muller, Ribery; Gomez.
Subs: Starke, Van Buyten, Rafinha, Shaqiri, Gustavo, Tymoshchuk, Pizarro.
Barcelona (4-3-3): Valdes; Alves, Pique, Bartra, Alba; Sergio Busquets, Xavi, Iniesta; Pedro, Messi, Sanchez.Subs: Pinto, Montoya, Abidal, Song, Thiago, Cesc, Villa.