World number two Muguruza swatted aside the 37-year-old 7-5 6-0 in July to claim her second grand slam title and next week's showdown will be the highlight of the White Group, which also includes Czech Karolina Pliskova and French Open holder Jelena Ostapenko.
The power-packed pool, full of aggressive players armed with big serves, will open proceedings on Sunday when Pliskova faces 2008 WTA Finals champion Williams, before Muguruza takes on Latvia's Ostapenko at the Singapore Indoor Stadium.
"Maybe I need to channel some of those memories (from 2008) to play well here... we have an amazing field, the tournament is the best it has ever been run and the excitement level is high," Williams said at the glitzy pre-tournament gala ceremony.
World number one Simona Halep was drawn in the Red Group alongside Ukraine's Elina Svitolina, Denmark's Caroline Wozniacki and in-form Frenchwoman Caroline Garcia, with play in that pool starting on Monday.
Halep will also have revenge in mind when she faces Garcia for the second time in three weeks after the Frenchwoman beat her in the China Open final in Beijing, a day after the Romanian became the 25th woman to climb to the top of the WTA rankings.
The elite event offers a healthy haul of points throughout the eight days of action and remarkably, seven players in the field, all excluding Garcia, have a chance to claim the prestigious season-ending number one ranking.
The round-robin format will see the top two players from each pool advance to the semi-finals.
Tournament preview
Draw:
Red Group (prefix denotes seeding)
1-Simona Halep (Romania)
4-Elina Svitolina (Ukraine)
6-Caroline Wozniacki (Denmark)
8-Caroline Garcia (France)
White Group
2-Garbine Muguruza (Spain)
3-Karolina Pliskova (Czech Republic)
5-Venus Williams (United States)
7-Jelena Ostapenko (Latvia)
(Reporting by John O'Brien; Editing by Pritha Sarkar)
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