The married pair topped the list compiled by Forbes magazine after collectively making $162 million between June 1, 2007, and June 1, 2008.
Hip-hop star Jay-Z pocketed $82 million from a 10-year deal with Live Nation, while Beyonce raked in $80 million from film, fashion and publishing deals.
Clinical psychologist and celebrity researcher Jim Houran said: "Naturally powerful people tend to gravitate toward other powerful people."
Will Smith and Jada Pinkett-Smith finished second place in the list, with earnings of $85 million.
Will was responsible for $80 million of the couple's fortune, most of which came from his roles in box-office hits 'I Am Legend', 'The Pursuit of Happyness' and 'Hancock'. Together the three movies made $1.2 billion at the box office, making Will Hollywood's most bankable star.
British couple David and Victoria Beckham were third with $58 million.
The soccer star has made $50 million since his highly-publicised move to the Los Angeles Galaxy team.
Although his salary from the club stands at $5.5 million, he boosted his income twofold by taking a cut of the team's ticket, merchandise and sponsorship sales. David made a further $35 million through endorsement deals.
Victoria earned $8 million thanks to her hugely successful Spice Girls reunion tour and clothing lines.
Other stars to make the top 10 include Brad Pitt and Angelina Jolie, Nicole Kidman and Keith Urban and Eva Longoria and Tony Parker.
The list takes into account money made from film, TV, and music projects, business ventures, endorsement deals and fashion lines.
Forbes magazine's list of Hollywood's Top-Earning Couples, top 10:
1. Jay-Z and Beyonce - $162 million
2. Will Smith and Jada Pinkett Smith - $85 million
3. David Beckham And Victoria Beckham - $58 million
4. Tim McGraw and Faith Hill - $35 million
5. Brad Pitt and Angelina Jolie - $34 million
6. Judd Apatow and Leslie Mann - $30 million
7. Gavin Rossdale and Gwen Stefani - $28 million
8. Keith Urban and Nicole Kidman - $25 million
9. Tony Parker and Eva Longoria - $22.5 million
10. Harrison Ford and Calista Flockhart - $22 million