The two appeared alongside one another in the hit NBC sitcom, which aired from 1994 to 2004 - but Paul feared his time would be cut short when he accidentally injured the actress during a break from filming.
"I was on the set for my first episode and Jennifer was on a Segway because she had broken her toe, and everyone was marvelling at it," he told U.K. chat show host Graham Norton. "Matt LeBlanc asked to have a go and immediately knew how to do it. I then asked to try it too. I spun round and rolled it right over Jennifer's foot!"
He added: "The producers look of panic was if to say, 'Is it too late to fire him? Has his character been established yet?' I felt awful. Such an inauspicious start."
While Paul was only hired for a short stint on the show, he ended up sticking around a lot longer, and even appeared in the iconic last episode - although he admitted he felt like he was "not supposed to be there".
Revealing another slip up he made with Jennifer, he remembered of their final day of filming: "I was on the sound stage and Jennifer Aniston was crying and I thought, 'I'm not supposed to be here', so to break the ice I went over and said: 'Well, we did it, what a ride.' The joke inevitably fell flat!"
However, there appears to be no hard feelings between the pair, as Jennifer went on to play Paul's wife in the 2012 movie "Wanderlust".