Per Us Weekly, Olivia Munn dated actor Chris Pine in 2009, right around the time Pine was gaining notoriety for his leading role in the rebooted "Star Trek." The couple reportedly dated for about five months, calling it quits in January 2010. While there isn't much info on the pair's former relationship, in 2012, Munn's phone was reportedly hacked and explicit NSFW text messages allegedly sent to Pine made their way around the web (via UpRoxx). Munn then dismissed the alleged texts on Twitter, jokingly tweeting alongside a meme and a picture of a cute baby, "If you ever hacked my phone, these are the pictures you'd find."

During an appearance on Whitney Cummings' podcast, "Good For You," in 2020, Munn also dished on the "worst sex" she's had with an unnamed ex-boyfriend, telling the comedian that her former flame defended his performance, saying, "Well, I just haven't had a lot of, you know, experience doing it" (via Mercury News).

Prior to getting together with Mulaney, Munn also dated "One Tree Hill" alum Bryan Greenberg for two years, reportedly had a three-day fling with Justin Timberlake, briefly dated "Glee" alum Matthew Morrison, and of course, had a high-profile romance with Green Bay Packers quarterback Aaron Rodgers (via Us Weekly), who famously went on to date Danica Patrick and is now engaged to "Big Little Lies" star Shailene Woodley.