In 2012, Levine appeared as a recurring character in American Horror Story: Asylum, the second season of the television series American Horror Story. He plays Leo Morrison, a newly-wed photographer visiting modern-day Briarcliff Manor, an insane asylum, on honeymoon with his wife, played by Jenna Dewan. The scenes were shot around his band's summer touring schedule. In an interview with E!, he said of his role: "It sounded like so much fun and that's why I wanted to do it ... this sounds, like, hysterical, funny, dark and cool and right up my alley". However, he admitted to not being a fan of the show nor horror genre in general, stating he didn't watch the episodes because "it's just so weird and disturbing".
In June 2012, Levine was cast in the musical romance-drama film Begin Again (originally titled Can a Song Save Your Life?). The film was directed by John Carney and Keira Knightley and Mark Ruffalo acted in the lead roles. In it, he plays Dave Kohl, Knightley's songwriting partner and former boyfriend of five years, who leaves her behind on finding success in the music industry. The film premiered at the 2013 Toronto International Film Festival to generally favorable reviews from critics.
Levine founded his own record label, 222 Records in February 2012. He stated that he was inspired to start the label to sign on Rozzi Crane, an USC music student he discovered through a mutual friend. She became the first singer signed on to the label, followed by Glee actor Matthew Morrison, Mexican artist Diego Boneta, and The Voice season 2 contestant and part of Team Adam, the singer Tony Lucca. It was reported that he was negotiating further with potential distributors, as well as organizing staff, to operate as a full-fledged record company with departments such as marketing, radio and publicity.
In September 2012, Levine was in the Philippines to collaborate with the clothing company Bench; they launched the menswear collection. In January 2013, Levine announced he would be enter a partnership with Sears Holdings to launch a multi-department lifestyle brand of apparel and accessories collections. The company owns Kmart and ShopYourWay, a shopping social platform; it also includes rapper Nicki Minaj in the same contract. The menswear collection was launched on October 1 that year and conducts business via 500 Kmart stores across the US, as well as online. In an official statement, Levine said: "Partnering with ShopYourWay to develop this line was an exciting opportunity for me and I am really looking forward to diving into the process of designing an apparel and accessory collection". In an interview with People, he commented further, "it was cool that they really promoted creative control. I like to be involved with process rather than just phoning it in". Later, Levine became a celebrity spokesperson for Proactiv. In the commercial, Levine shares details about his acne experiences in high school, and promotes Proactiv Plus.
In May 2012, Levine began dating Behati Prinsloo, a Namibian Victoria's Secret model. The couple married on July 19, 2014, with Jonah Hill officiating the wedding. Levine and Prinsloo have two daughters, Dusty Rose (born September 21, 2016) and Gio Grace (born February 15, 2018).