Louis, who was born at Twycross Zoo, was one of the original PG Tips chimps, and parodied James Bond in the adverts for the tea.
The chimp died aged 37, after a short illness, the zoo confirmed.
Zoo curator Dr Charlotte Macdonald said: “Louis was a very gentle and laid-back chimp - a favourite with everyone.
“Born at Twycross, he was one of the original PG Tips chimps.
“Although gone, Louis will never be forgotten - he will always be a member of our Twycross Zoo chimp family.”
Louis’ mate Choppers, who also appeared in the adverts, remains at the zoo.
Dr Macdonald added: “[Choppers] is doing well and will be monitored closely over the next couple of weeks by the animal team.
“She will be introduced to some of the other chimps in the near future.”