James Corden will present the show for his fifth and final time from the O2 in London on February 19.
The 'Unconditionally' singer said: "The Brits has always showcased the music that I love and am influenced by. It's an honour to play at such a prestigious event where musicality shines at its brightest."
Perry won the award for Best International Female in 2009.
Meanwhile, the Sheffield-based Arctic Monkeys have bagged five gongs since 2006, including Best British Breakthrough, as well as Best British Album and Best British Group for two consecutive years in 2007 and 2008.
Brit Awards chairman Christian Tattersfield said: "We are extremely ambitious for the 2014 show, showcasing global superstars and celebrating the incredible success of British music.
"We are going to pull out all the stops to make this the biggest and most exciting Brits ever."
Tickets for the ceremony go on sale from 10am today (November 28).
Watch Sir Ian McKellen present the Arctic Monkeys with the Best British Group award at the Brits 2008 below: