Johansson endorsed the Calvin Klein perfume "eternity Moment" and was featured in several commercials and printed advertisements for the product. One of the commercials was featured in Scarlett Johansson's 2005 film The Island. Further establishing Scarlett Johansson's position in Hollywood, Scarlett Johansson became the face and spokesperson for the French luxury brand Louis Vuitton in early 2005 and in January 2006 was named the spokesperson of L'Oreal.

Johansson appeared on the controversial cover of the February 2006 issue of Vanity Fair in the nude with fellow Hollywood "it girl" Keira Knightley and world-renowned fashion designer Tom Ford. In March of 2006, Scarlett Johansson topped the U.S. edition of FHM's poll of the sexiest women alive (in the UK edition Johansson was third). In May of 2006, Maxim named Johansson #6 in their Hot 100 issue, and in July of 2006, Reebok signed a deal with Johansson to co-create "Scarlett 'Hearts' Rbk", athletic footwear scheduled for a debut in the spring of 2007. Johansson will also be featured in Reebok's global women's advertising campaign, also in the spring of 2007. The company's press releases described Johansson as a "world renowned style icon" and an "inspiration for today's young women". In November 2006, Johansson was named "Sexiest Woman Alive" by Esquire magazine.

In 2006, Johansson starred in a short film directed by Bennett Miller and set to Bob Dylan's "When the Deal Goes Down...", released to promote Dylan's album, Modern Times. Between 2005 and 2006, Scarlett Johansson also sang the track "Summertime" for Unexpected Dreams - Songs from the Stars, a non-profit collection of songs recorded by Hollywood actors, and was in talks to appear in a stage version of The Sound of Music.

In October 2006, Fox News reported that Johansson has signed to record a music album with Rhino Entertainment's Atco Records, with a possible release date of Spring 2007. The album, entitled Scarlett Sings Tom Waits, will consist entirely of Johansson's cover versions of Tom Waits songs. Johansson is also the leading lady in the Justin Timberlake music video "What Goes Around...".