EXCLUSIVE: 'Bachelorette' Couple Kaitlyn Bristowe and Shawn Booth Play 'Who Wants to Be a Millionaire'

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Bachelorette couple Shawn Booth and Kaitlyn Bristowe are putting their trivia knowledge to work for their favorite charity.

Starting Monday, Who Wants to Be a Millionaire will run a week-long special called "Bachelor Fan Favorites," where some of the most popular alumni from the reality series will compete for the grand prize.

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Fortunately for the contestants, there will be a friendly, familiar face on set as Bachelor host Chris Harrison will be asking the questions. The last time we saw Harrison with Booth and Bristowe, the young lovebirds were getting engaged on The Bachelorette season 11 finale. Still, he doesn't seem to have full faith in the couple when it comes to trivia.

"Kaitlyn and Shawn are probably going to be a train wreck," Harrison jokes in a behind-the-scenes interview. "You know a dumpster fire? You know you should really run by the dumpster fire, but you can't. You have to stop and watch the dumpster fire. That will be Kaitlyn and Shawn. I have no doubt."

"It totally helps that Chris is the host, because he makes everyone feel so relaxed, even though he just called us a dumpster fire," Bristowe says.

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Booth and Bristowe will face off for the charity Pet Orphans of Southern California, an organization dedicated to promoting responsible pet ownership, rescue and rehabilitation of animals.

They could make a lot of animals happy if they win the million-dollar prize, and they could put a smile on a lot of human faces too, based on a promise Booth makes in an exclusive clip.

"If we get the million dollars today, we'll pick a [wedding] date," he says.

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Other Bachelor faves signed up to play are J.P. and Ashley Rosenbaum, season four star Deanna Stagliano and season seven's "Prince Farming," Chris Soules, but how would Harrison feel about giving the villain "Bad Chad" a try at the game?

"I would really love the Chad to be out here playing Millionaire," he says. "I think he would get to that $500 question -- the very first one -- not like it, and then choke me out. And that would be the episode."