On June 3, 2010, Munn debuted in her new role as a correspondent on Comedy Central's The Daily Show. Her hiring prompted criticism from Irin Carmon of Jezebel, who questioned Munn's credentials and said the show's production was sexist for hiring Munn, whom Carmon said was a sex symbol. Carmon said Munn's hiring was a perpetuation of the show production office's history as a male-dominated atmosphere marginalizing and alienating to women. A group of thirty-two female Daily Show production staff members said Carmon's piece was inaccurate and misinformed. Munn said that Carmon's assertion was an insult both to her and to the rest of the Daily Show staff. She went on to appear in 16 more episodes as a correspondent, with TV Guide naming her signature segment "Tiger Mothering," in which she mocked the high expectations of Chinese mothers, in part by interviewing her own mother. Her last episode as a correspondent aired September 2, 2011. She returned for a brief segment in host Jon Stewart's final show on August 6, 2015.
In 2010, Munn guest-starred on NBC's comedy-drama Chuck as a CIA agent. In 2011, Munn appeared in the comedy film I Don't Know How She Does It (2011) as Momo. In 2012, Munn had a leading role in The Babymakers, a minor role in Freeloaders, and appeared in Magic Mike, directed by Steven Soderbergh. She also appeared as Angie, Nick's stripper girlfriend, in three episodes in Season Two of FOX's sitcom New Girl.
Munn's book Suck It, Wonder Woman: The Misadventures of a Hollywood Geek ( ISBN 978-0-312-59105-2) was released on July 6, 2010. In a review for Time Out New York, Olivia Giovetti said that the book offers glimpses into Munn's life, but does not go into depth.
Munn helped PETA with a campaign that ultimately freed an ill elephant from a touring circus. Her blog for The Huffington Post was credited with encouraging fans to contact the USDA on the elephant's behalf. Munn posed for PETA's "I'd Rather Go Naked Than Wear Fur" campaign in April 2010, and again in January 2012. In February 2013, Munn fronted a PETA release of new footage showing cruelty to animals in Chinese fur farms.