Following the release of the album, Marling revealed that she only listened to "music made between 1969 and 1972" during the songwriting process for the album, and described it as an era when "guitar was becoming a kind of masculine extension". Marling explained during the post-release promotional period that she sought a minimalist approach for the fourth album and, in contrast to the previous two albums, recorded all of the songs without a band.

She was invited to tour with Jamie T after he attended her second solo gig. She has toured with a number of other Musicians including Adam Green from the anti-folk band The Moldy Peaches. She performed at the 2007 O₂ Wireless Festival and performed at the first Underage Festival in August 2007 at Victoria Park, East London, before releasing her debut EP "London Town" on WayOutWest Records.

Marling dated Noah and the Whale singer/guitarist Charlie Fink briefly before the pair separated in 2008. She also dated Marcus Mumford of Mumford and Sons until late 2010. She moved to Silver Lake in Los Angeles, California in 2013, before relocating back to London in December 2014.

The follow-up to Alas, I Cannot Swim, titled I Speak Because I Can, was released on 22 March 2010. Produced by Ethan Johns, the album has a more mature sound and lyricism, dealing with "responsibility, particularly the responsibility of womanhood". The album is preceded by the singles "Goodbye England (Covered in Snow)", released on iTunes in December 2009 and "Devil's Spoke" on 15 March 2010. On 28 March 2010, I Speak Because I Can entered the UK Albums Chart at Number 4. It was nominated for the 2010 Mercury Music Prize. In 2013, NME listed the album at 263 in their list of the 500 greatest albums of all time.

Marling's third album, A Creature I Don't Know, was released on 12 September 2011. The album received positive reviews and reached number four on the UK album charts.

In September 2013, Marling explained: "I am a solitary person but I love people, I’m not a misanthrope. I like the idea of speaking only when it's strictly necessary. The closest I ever feel to people is in shared experience. I’m still exploring that, I don’t know where it's going to lead me."

On 16 December 2014, Marling announced that her fifth studio album would be titled Short Movie, and its title track, released on the same date, is the lead single and was made available for digital download. The album features 13 songs composed by Marling and was released in the UK on 23 March 2015 and one day later in the US.

Marling co-stars in the short film, "Woman Driver", which was filmed in Marfa, Texas and directed by Chris Perkel. The movie was shot and edited in 72 hours. Marling later won "Best Actress" at the 72-Hour National Film Challenge. The film was shown at the London Short Film Festival on 14 January 2015 and later premiered on Vimeo the following month. The film also featured new music from Marling.

In a tweet, Blake Mills confirmed that Marling's sixth studio album was completed. In November 2016, Marling announced the release of Semper Femina in March 2017, with "Soothing" the first single from the record. The album was released to critical acclaim. Marling received her first Grammy nomination for Best Folk Album for Semper Femina, but did not win the award. Semper Femina was also nominated for IMPALA's European Album of the Year Award.

Marling covered "Red Right Hand" by Nick Cave and the Bad Seeds and "A Hard Rain's a-Gonna Fall" by Bob Dylan for the season 4 finale of Peaky Blinders which aired on 20 December 2017.

Marling was born in Berkshire, England, the youngest of three daughters. Her mother is a music teacher; her father, Sir Charles william Somerset Marling, the 5th Marling Baronet, ran a recording studio, introduced her to folk music and shaped her musical taste, an experience that Marling later described as, "a bit of a blessing and a bit of a curse....[because] I couldn’t slot myself into the age-appropriate genre". She learned guitar at an early age.