The 56-year-old singer will stoke anticipation for her upcoming 13th studio album, Rebel Heart, to be released on March 9, reported Guardian online.
Announcing the news on Instagram, Madonna posted an image of Tracey Emin's Brit statuette with black wire across its face with the caption, "Hello to all my UK Rebel Hearts! See you at the Brits on Feb 25th #BritsImMadonna #livingforlove #rebelheart."
Brits chairman Max Lousada said they are "delighted" to bring Madonna back to the awards.
The pop star has won two Brits, the first in 2001 and the second in 2006, both for best international female. Her last appearance at the Brits was in 1995, when she performed 'Bedtime Stories' while dressed in white and accompanied by a wind machine.
Brits awards 2015 will take place on February 25 at London's O2 arena.
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