A total of 22,141 fans wore the caps in London’s Hyde Park on Friday ahead of his set at the British Summer Time (BST) festival.
Many also sported other elements of the singer’s signature style — a suit, black aviator sunglasses and stick-on dark goatees.
“Record breaking, record making, history in the making,” the 45-year-old hip hop artist said before being presented with his certificate.
“Thank you London, thank you to the fans, thank you Hyde Park, thank you to the bald-es,” he added, as temperatures reached 31C in the British capital.
In recent years, it has become a trend for fans to dress as Pitbull while attending his performances.
“I think I put it (the bald cap) on too early,” 21-year-old student Connie McGovern told AFP.
“I can’t take it off now because my hair and my make-up’s messed up, so I’ve got to commit — it’s not coming off.”
Her sister Ella, 23, said it was “good to be a part of something”.
“We’re going to make history today,” she added.
Pitbull was the first person to attempt the feat under official adjudication, meaning there was no previous record to beat.
The Miami-born star’s hits include “Fireball”, “Timber”, “Time Of Our Lives”, and “On the Floor”.