Millionaire, which was originally presented by Chris Tarrant, is returning for seven new episodes to air across one week in honour of its 20th anniversary.
Grand Tour presenter and Clarkson said: "I have always loved the show and am thrilled to be involved with its rebirth.
"I'm a big fan of quiz shows and I'm looking forward to hosting this iconic TV show and hopefully making a few millionaires!"
The popular ITV game show debuted in September 1998 and went on to become one of the most popular TV formats across the world, spawning versions in countries including America, India, Australia, Japan and Russia, and it also inspired Danny Boyle's Oscar-winning film Slumdog Millionaire.
PAJeremy Clarkson will be the the new presenter of Who Wants To Be A Millionaire?
I have always loved the show and am thrilled to be involved with its rebirth
The programme saw members of the publicatempting to answer increasingly difficult questions in order to win up to a million pounds.
Each hopeful millionaire would be given three lifelines to help them answer tricky questions - phone a friend, ask the audience and the 50/50 option.
One of the show's most memorable moments came in 2003, when Army major Charles Ingram was found guilty of cheating his way to the top prize by using a coughing accomplice in the audience.
Millionaire was a ratings success for ITV, with one episode in 1999 pulling in more than 19 million viewers.
GETTYChris Tarrant was the host for 15 years but left in 2013
In 2013, after 15 years as the host, Tarrant made the decision to leave, and the final episode aired in February 2014.
The new episodes, which are set to air later this spring, will include a number of new twists and turns for audiences to look forward to, ITV has said.
ITV's head of entertainment Siobhan Greene said: "It felt like a no-brainer to celebrate the show that was a trailblazer of its time and broke the mould.
"In doing this one-off special week, I hope Millionaire will be introduced to a whole new generation. And with TV legend Jeremy Clarkson asking the questions, frankly anything could happen. I can't wait."