The Spain midfielder has spoken of the perils that await his side at the Allianz Arena on Wednesday, highlighting Los Che's ability to exert pressure on their opponents
The 2001 finalists will lock horns on Wednesday in Group F's curtain-raiser on the back of contrasting fortunes, as the Bavarians finished runners-up in last season's competition, while Los Che were dumped out at the group stage.
And Martinez, who has vast experience of playing Valencia from his time at Athletic Bilbao, expects the Liga outfit to pose a considerable threat to his new team, even at the Allianz Arena.
"I know [Valencia] very well and I've played them quite a few times," he told Bayern's official website. "They'll definitely push us hard because they have a great team.
"They're very balanced, they have plenty of pace, they put opponents under pressure, and they're very well set-up tactically."
The 2012-13 edition of the Champions League will be Martinez's first of his career, and he is relishing the prospect of making his bow in Europe's elite club tournament.
"I've never played in the Champions League before," he added. "It's an important match for us.
"Bayern made it to the final last season, and we're among the favourites for the competition, so we obviously want to make a successful start."
Kick-off in Bavaria is scheduled for 20:45CET.