The Brazilian-born beauty, who is the face of the high street retailer's Autumn/Winter 2013 campaign, poses on the streets of London in a series of knitwear, coats and jeans.
She took to Instagram to share a snapshot of her new modelling gig with her followers. "New H&M campaign," she wrote alongside the close-up image of her staring into the camera.
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The mother-of-two is the latest high profile name to sign on with H&M. She follows in the footsteps of Beyonce, who starred in the Swedish label's summer adverts, and David Beckham, who created his own underwear line with H&M.
It's not the first time Gisele has worked with the brand – she starred in their spring/summer 2011 campaign, which famously had to have additional clothing added digitally to ensure it was appropriate for use in the Middle East.
Last year, Gisele was named the highest-earning model for the sixth year running, with estimated earnings of $45million (£29million).
Gisele is married to American footballer Tom Brady. They began dating in December 2006 after being set up on a blind date by a mutual friend.
They tied the knot on 26 February 2009 in a small Catholic ceremony in California. They remarried in a larger ceremony in Costa Rica in April of the same year.
The couple have two children together – son Benjamin Rein Brady and daughter Vivian Lake Brady.