The chat show host and her professional partner earned 23 points for their thrilling jive from show judges Carrie Ann Inaba, Bruno Tonioli and Len Goodman, with army veteran J.R. Martinez – paired with Karina Smirnoff – and former 'The Hills' star Kristin Cavallari and her partner Mark Ballas coming joined second with a score of 22.
Last week's top scorers Chynna Phillips and Tony Dovolani tied in third place with 21 points alongside Elisabetta Canalis – the ex-girlfriend of George Clooney – Nancy Grace and Rob Kardashian.
Prior to the episode, Rob admitted he was struggling to be around the show's professional dancers as he is currently "insecure" about his weight.
He said: "I'm scared as hell. The jive is pretty hard for me because I don't feel great about myself at all. To be in front of a bunch of people knowing like I'm insecure with my weight, and I say I have man boobs jokingly, but it's true.
"Being surrounded by all these dancers who are in great shape, it's just hard to be around and then put yourself out there like that."
However, his fears were quickly abated when Carrie told him he was a better dancer than his older sister Kim Kardashian – who was eliminated in the third week when she appeared on 'Dancing with the Stars' – as he has the "dancing gene".
She said: "It's official. Rob Kardashian is a better dancer than Kim Kardashian! No disrespect to Kim, but you have the dancing gene, honey. It's nice to see your confidence coming out."
Hope Solo and Maksim Chmerkovskiy earned a score of 19, while David Arquette and his partner Kym Johnson tied with Carson Kressley and Anna Trebunskya with a score of 18.
Chaz Bono and his partner Lacey Schwimmer rounded off the scoreboard in bottom place with a mark of 17.
Bruno said: "There is a likeability about you, Chaz. It was like watching a little Ewok dance with Princess Leia. It’s cute and it’s lovely, the problem is the quickstep has to be fast.”