Williams now holds more than twice as many points as No. 2 Maria Sharapova.
Bouchard slipped from 12th to No. 26 after a straight-sets loss to Chinese qualifier Ying-Ying Duan. The native of Westmount, Que., who finished the 2014 season ranked seventh in the world, has struggled in 2015, posting just four wins since the Australian Open in January.
Novak Djokovic's third championship at the All England Club allowed him to retain his healthy lead atop the ATP rankings on Monday over No. 2 Roger Federer, the man he beat in the final.
Sharapova, who lost to Williams in the semifinals, rose two spots, while last year's champion, Petra Kvitova, slid from No. 2 to No. 5 after exiting in the third round.
Garbine Muguruza, the 21-year-old from Spain who was the runner-up to Williams, moved into the top 10 for the first time at No. 9, an 11-spot rise.
The men's top 10 remained unchanged, including Andy Murray at No. 3, Canadian Milos Raonic at eighth and Rafael Nadal at No. 10.
Vancouver's Vasek Pospisil rocketed up 27 spots to No. 29 after making the quarter-finals at Wimbledon.