Charlize Theron, Sean Penn

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Charlize Theron and Sean Penn will soon be spending a lot more time together.

After all, it was recently reported that the lovebirds are teaming up on the upcoming movie, The Last Face. Penn will direct Theron in the African drama, which will also star Javier Bardem.

According to Deadline, Theron will play a doctor who is doing humanitarian relief work in Africa amidst violent political conflicts in the region. She meets another doctor (Bardem) who is doing the same work, and the story revolves around tough moral decisions that must be made during a time of civil unrest.

The professional pairing of Theron and Penn got us thinking about other real-life couples who decided to mix business with pleasure...

Eyes Wide Shut, Tom Cruise, Nicole Kidman

Moviestore Collection/Rex/REX USA

1. Tom Cruise & Nicole Kidman: After meeting on the set of 1990's Days of Thunder, the two tied the knot shortly thereafter. As a married duo, they went on to costar in 1992's Far and Away and, as shown above, in Stanley Kubrick's final film Eyes Wide Shut in 1999. Cruise and Kidman later divorced in 2001.

Scooby - Doo, Sarah Michelle Gellar, Freddie Prinze Jr.

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2. Sarah Michelle Gellar & Freddie Prinze Jr.: Sparks flew (amid all the blood being splattered) between these two when they made 1997's I Know What You Did Last Summer. They later got hitched in 2002 and subsequently appeared together as Daphne and Fred in Scooby-Doo and its sequel, Scooby-Doo 2: Monsters Unleashed.

Ali, Jada Pinkett Smith, Will Smith

Moviestore Collection/Rex/REX USA

3. Will Smith & Jada Pinkett Smith: Married since 1997, the happy couple got around to working together in the 2001 Michael Mann-directed biopic Ali, in which Will played the title role of the famed boxer and Jada portrayed the champ's first wife, Sonji Roi.

Overboard, Kurt Russell, Goldie Hawn

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4. Kurt Russell & Goldie Hawn: Even though they initially met while shooting 1968's The One and Only, Genuine, Original Family Band, it wasn't until after they teamed up again on 1983's Swing Shift that they became a couple. Make that one of the most enduring couples in Hollywood. They starred alongside each other in the 1987 romantic comedy Overboard.

Zoolander, Ben Stiller, Christine Taylor

Moviestore Collection/Rex/REX USA

5. Ben Stiller & Christine Taylor: After exchanging vows in 2000, the couple went on to crack us up in Zoolander (2001), Dodgeball: A True Underdog Story (2004) as well as Tropic Thunder (2008).

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