With Real Madrid, the two-time defending champions, and Apoel Nicosia, the Cypriot minnows, making up group H, Dortmund are widely expected to be Tottenham's most direct competitors for qualification.
Particularly with Dortmund's current injury issues, Pochettino should snatch at the chance to give Tottenham an early advantage at progressing to the knockout rounds.
"It's true that in theory Real Madrid are first, then Dortmund, Tottenham and APOEL compete to be second".
Defeat to eventual semi-finalists Monaco was followed by a 1-0 reverse against Bayer Leverkusen, forcing the north Londoners to settle for a place in Europa League.
The VAR is being trialled in Germany this season and this was the first time an intervention led to a player being sent off.
Spurs are playing all their home games at Wembley this season, as they prepare to move into a new ground next year.
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He added: "Of course the final we played here at Wembley is still a painful memory, but excitement is the overriding emotion".
"When you are here (in England), the Premier League is the main competition for every player".
"I think it's so important to try to win the first game and get three points".
"We know very well what the competition demands from you, and I think it is so important, that experience from last season".
Nuri Sahin was part of the Dortmund team beaten by Bayern, but he is similarly looking forward to the game at Wembley.
"But we've got a fantastic squad so whoever comes in will be ready". "It will definitely give us confidence if we go out and get results against teams like Dortmund".
"With Wembley, we need to adapt our game", said boss Mauricio Pochettino.
"We're in a tough group but it's a good test for us, and the players are excited to play against the best teams in Europe".