The beauty campaign is a first for the Gossip Girl actress, who was the spokesmodel for Chanel's Mademoiselle handbags line in 2011.
"Gucci is a staple. It is a brand I have always looked up to because to me it represents strength," Lively told WWD.
"In their designs, in their images, in what they stand for philanthropically, and especially in their fragrance... I couldn't be more proud to be working with Gucci and its heart, Frida."
Gucci Première, said to be "infused with Old Hollywood charm", will be made available in in late July in the UK and worldwide in September.
Drive director Nicolas Winding Refn has shot an advert for television, while the print advert was taken by fashion photographers Mert Alas and Marcus Piggott.
Lively can be seen next in Savages opposite Taylor Kitsch and Aaron Johnson, out in theaters on July 6 in the US and on September 28 in the UK.
Watch a trailer for Savages below: