The new note was cleaner and stronger as it was more resistant than the older version, said Bank of England Governor Mark Carney, EFE news reported.
"The use of polymer means it can better withstand being repeatedly folded into wallets or scrunched up inside pockets and can also survive a spin in the washing machine," Carney said.
The note, which is more difficult to fake according to the bank, would only be available at some banks and ATMs to begin with, but the majority of banks were expected to have it within a week.
The first cities to have accessed the new note were London, Manchester, Leeds, Hull and Cardiff.
Old 5 pound notes would be valid until May 5, 2017.
Plastic 10 pound notes ($13.32) featuring the writer Jane Austen and 20 pound notes ($26.64) with the face of painter J.M.W. Turner are expected to be introduced by 2020.
