The 37-year-old Williams advanced from the White Group along with Czech Republic's Karolina Pliskova, who lost to French Open champion Jelena Ostapenko 6-3, 6-1.
Karolina Pliskova comfortably beat Garbine Muguruza 6-2, 6-2 in the round-robin stage to book a place in the semifinals of the showpiece event.
The Russian tennis ace defeated Belarusian teenager Aryna Sabalenka 7-5, 7-6 (8) on Sunday to move from 86th to 57th in the latest WTA rankings.
Playing in her first tournament since earning the WTA's top ranking, Wimbledon champion Muguruza had 29 unforced errors to drop the final 10 games of the match.
Despite an early loss to Petra Kvitova in the last 16 of US Open, Muguruza topped the WTA rankings for the first time in her career dethroning Czech Republic's Karolina Pliskova.
Muguruza becomes the 24th woman overall to hold the number one ranking and the second player representing Spain to achieve this historic milestone.
Halep will become World No.1 for the first time if she can defeat Muguruza to capture her maiden title in Cincinnati.
Nadal was sloppy at the outset and on the defensive for much of a 6-2, 7-5 loss that lasted an hour and 20 minutes.
The former World No.1 was also scheduled to play at the Rogers Cup in Toronto this week but withdrew because of injury.
After clinching the Wimbledon titles, Roger Federer notches up to No.3 rank in the ATP while Muguruza enters the top ten with a No.5 position in the WTA.
The 23-year-old has struggled in the periods between her successes at Grand Slam level and outside of tennis. The Spaniard has won 2 major titles and has just appeared in two finals.
"It's great to go out there and play somebody that you admire," Muguruza said after her famous win over Venus Williams in Wimbledon final.
With Garbine Muguruza defeating her role model Venus Williams to claim the Wimbledon title, Roger Federer faces Marin Cilic to set a record at the All England Club.
Spain's Garbine Muguruza out-powered Venus Williams in straight sets to win her first title at the All England Club in London.
At 37, Venus Williams becomes the oldest finalist at the All England Club since Martina Navratilova who finished as runner-up in 1994 at that age.
The 14th-seeded Spaniard advanced to the final at the All England Club by beating Magdalena Rybarikova in straight sets by 6-1, 6-1 Thursday on Centre Court.
Three-time Wimbledon champion Djokovic beat Adrian Mannarino in straight sets 6-2, 7-6 (5), 6-4 in the fourth-round match at All England Club Championship in London.
World No.1 Angelique Kerber advanced to the second round at Wimbledon defeating American Irina Falconi 6-4, 6-4; Muguruza passes Alexandrova's test.
London: Game. Set. Serena Slam.Serena Williams overcame a slow start, eight double-faults and a nervy finish to beat Garbine Muguruza 6-4, 6-4 on Saturday for her sixth Wimbledon title, fourth Grand Slam championship in a
London: Turn back the calendar more than a year, to June 28, 2014, when Serena Williams lost to Alize Cornet in the third round at Wimbledon.It was Williams' earliest exit from the All England Club
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