A sizzling shot from Toni Kroos quarter of an hour from time secured three points for the hosts, who had taken the lead before the interval through Bastian Schweinsteiger
Jupp Heynckes’ side were the dominant side throughout but were forced to be persistent to break down the Spaniards, who were rarely able to exert themselves as an offensive force.
It took the Bavarians nearly 40 minutes to open the scoring, with Bastian Schweinsteiger, who missed the crucial penalty as FCB lost on spot kicks against Chelsea in last year's final, driving home to exorcise some of those demons. Although the hosts were not so impressive after the break, Toni Kroos hammered a second to secure the points.
Nelson Valdez's late header gave the score a sense of respectability for the visitors, but his effort came too late to make a change to the outcome. Indeed, matters got worse for Valencia in stoppage time, with Adil Rami dismissed after conceding a penalty that was missed by Mario Mandzukic.
Bayern had made a positive start to the match without being overwhelming. They dominated possession and territory, but struggled to really worry Diego Alves, apart from a three-minute spell in which the home side drove three well-struck shots at goal that the custodian dealt with solidly.
Arjen Robben was regularly able to make his trademark jink inside from the right wing to aim at goal with his left foot, and after loose play in the visiting rearguard he had a shot deflected just over, 10 minutes before the break.
Shortly afterwards, Valencia mustered their first even remotely meaningful attack, but in pushing players forward the Spaniards allowed Bayern room in which to attack, and the Germans punished them with Robben unselfishly playing in Schweinsteiger to drive home from the right side of the box.
After the interval, Mauricio Pellegrino’s men showed a more forthright attitude and at least mustered some spells of pressure against opponents who allowed their passing to become a little scrappy.
Manuel Neuer was never unduly troubled, but at least Tino Costa’s long-range efforts gave the goalkeeper something to do.
At the other end of the field it was Kroos who was impressing. The Germany international had strong claims for a penalty waved away. Then he fired a fierce shot at goal from just outside the area that required an athletic save.
With quarter of an hour remaining, he finally sealed the game, driving a powerful shot into the top corner having been allowed far too much room on the edge of the box.
There was still time for late drama, with Valdez heading Valencia back into the game before Mario Mandzukic missed a stoppage-time penalty after Rami was dismissed for a foul on Robben.
Bayern had already done enough to secure three points, taking a successful first step in the competition.