The celebrity couple's professional and personal lives earned them the top power acting spots in the 2009 Guinness edition, the record-keeping group said in a news release Sunday.
Jolie previously split the honor with fellow Hollywood star Jennifer Aniston, while actor Tom Cruise's four-year reign as Most Powerful Actor ends at the hands of Pitt.
Guinness officials determine the Most Powerful categories based on a number of factors, including Internet searches and financial earnings.
The 2009 edition of the annual records book also names "Lost" as the Most Downloaded TV series, although the ABC drama lost its Most Popular TV Show crown to Fox's "House."
The newest edition of the record publication is due out in stores Wednesday.