The event takes place in Hyde Park on September 8, the same evening as the traditional Last Night of the Proms in the nearby Royal Albert Hall.
The 'All the Lovers' star will be accompanied by the BBC Concert Orchestra for the performance.
Minogue said of her appearance: "I'm delighted to be performing at one of the UK's most outstanding nights of the musical calendar, and to sing in front of thousands of people whilst being accompanied by the legendary BBC Concert Orchestra in such a special year is truly a dream come true."
Other acts on the lineup include Il Divo and tenor Alfie Boe, while Sir Terry Wogan and Tony Blackburn will host.
Wogan said: "To have the Princess of Pop herself, Kylie Minogue, performing in Hyde Park promises to make the concert an unforgettable spectacle."
Minogue drew crowds in London recently while filming in denim hot pants, a leather biker jacket adorned with a giant red heart, and a pair of large sunglasses.
Watch a tour clip of Minogue performing 'Spinning Around' below: