The veteran rocker, 75, will join previously announced acts including Stormzy, Lizzo, Lewis Capaldi, Harry Styles, Billie Eilish and Dave in performing at the event.
The singer has performed at the Brit Awards once before, in 1993, when he also picked up an outstanding contribution award.
Out of hospital
Last year Sir Rod celebrated his 10th album reaching number one in the UK charts, after the release of You're In My Heart.
He also became the oldest male solo artist to have a number one album in the UK.
The singer was discharged from hospital last month after undergoing knee replacement surgery.
The ceremony, which is being hosted by comedian Jack Whitehall and broadcast on ITV, will take place on February 18 at London's O2 Arena.