The 46-year-old was named as the successor to Ronald Koeman back in August following a disappointing World Cup performance from the Netherlands.
Klopp took the Germany job in similar circumstances and the two are now set to meet at the Johan Cruijff Arena for their Nations League clash.
Xavi is the first foreign coach of the Netherlands since Ernst Happel in 1977-1978, and he is keen on going head-to-head with former Liverpool boss Klopp.
"We have to play our best football tomorrow because Germany are a great team," Xavi told reporters.
"I can feel this rivalry. Everyone in our team is really looking forward to the game, and it is a great way for us to start this journey.
"He (Klopp) has been one of the best coaches in the world in recent years. It will be a great challenge for the whole team and for me personally.
"It is always the goal to win, but it is even more important to leave a good impression with the execution. I want the team to show passion, ambition, desire and our philosophy."