Her second single, "Your Love's a Drug", was digitally released on March 30, 2010, and she is also featured on Stephen Jerzak's song "She Said". Meester did a duet with DJ Clinton Sparks on "Front Cut", which appeared on the internet in February 2011. Lil Wayne worked with her on an unreleased song titled "Make It Rain" and Jesse McCartney wrote another song. The album was produced by Polow Da Don, Harvey Mason Jr., and Spencer Nezey. Meester began working on it in March 2009 and the album was initially projected to be released in the fall of 2009, but was later delayed to early 2010. It was pushed back again to late 2010, and was ultimately shelved.
Meester had small roles in the comedies Date Night and Going the Distance. She then starred with Gwyneth Paltrow and Garrett Hedlund in the country music drama Country Strong. Wesley Morris of The Boston Globe described Meester as the best part of the film, writing, "She's just doing Reese Witherspoon's June Carter Cash in Walk the Line with dabs of Miley Cyrus and Kellie Pickler. But it's not an impersonation; it's a performance with its own comedy and sweetness." Claudia Puig of USA Today was also positive, stating "Meester shows she can do more than play one of Gossip Girl's privileged Manhattan socialites." For the film, Meester recorded a cover of the song "Words I Couldn't Say" by Rascal Flatts as well as "A Little Bit Stronger" by Sara Evans featured on the film's soundtrack; a promotional single titled "Summer Girl"; and a duet with Garrett Hedlund titled "Give In To Me". After wrapping, she received a guitar from Tim McGraw and decided to learn how to play it. In October 2010, Meester said she had been working with a band called Check in the Dark and had been writing for the last six months after being inspired by Country Strong. She revealed her influences, "I love Neil Young and Joni Mitchell, that style of music, and as far as songwriting I think that's where my heart is."
In 2010, Meester signed on to be the spokesperson for Herbal Essences hair products. In the same year, she took part in Bulgari's humanitarian efforts for the Save the Children organization with Isabella Rossellini and Maribel Verdú. She next fronted a beauty campaign for Korean brand eSpoir. Vera Wang selected her to be the face of the fragrance Lovestruck in 2011, stating that Meester's "beauty, talent and spirit will inspire all the young women that I hope will enjoy this passionate, new young fragrance." The next year, Meester shot a campaign for the follow-up fragrance, Lovestruck Floral Rush. Italian fashion house Missoni named Meester the face of their spring/summer 2011 campaign.