The 60-year-old actor will donate the winning amount to Pengeulan Primary School in Wales, a facility he visited in September, reported Daily Star online.
He seems nervous about facing the string of questions on the show.
"I just hope I can win some big bucks for them. One minute I am terrified, the next I can't wait to jump in to the seat. I have been gearing up and I am ready to face the million pound question," said Hasselhoff.
The actor will dress up like Captain Hook, a character from children's story 'Peter Pan'.
