Greaves arrives in Wolverhampton on the back of a record-breaking year on the PDC Women's Series, having gone unbeaten in 86 matches and claimed 18 titles from 24 events - the most dominant season in the competition's history.
At just 21, and with a high-profile recent victory over defending champion Luke Littler under her belt, she will now test herself against one of darts' modern giants.
Van Gerwen, currently ranked world number three, averaged 115.19 in the 2021 Grand Slam - the second-highest mark ever recorded at the event - and despite some indifferent form this year, remains a consistent threat in any field.
MVG and Greaves make up part of a star-studded Group G, which also features a fascinating encounter between two-time runner-up Gary Anderson and Germany's rising star Niko Springer.
Littler looks to defend title
Reigning Grand Slam and World Champion Luke Littler begins his title defence on Saturday evening, facing Czech number one Karel Sedlacek in Group E.
Littler, who lifted the Eric Bristow Trophy last year aged just 17, has since become one of the sport's global stars, winning five PDC titles in 2025 and averaging over 99 across televised matches this season.
World number one Luke Humphries opens his campaign in Group A against CDC Continental Cup winner Alex Spellman, as he sets out in pursuit of a second Grand Slam crown.
The group also sees 2022 champion Michael Smith face Nathan Aspinall, revisiting the same clash that decided the Wolverhampton final three years ago.
Elsewhere, three-time winner Gerwyn Price opens his Group D campaign against Tour Card qualifier Ricky Evans.
The Welshman, whose overall Grand Slam average sits above 98 across his 48 matches, shares a group with veteran James Wade and Swiss debutant Stefan Bellmont - the first player from Switzerland ever to appear in the tournament.
Group F offers another compelling subplot, with newly crowned European Champion Gian van Veen meeting Women's World Matchplay title-holder Lisa Ashton.
They are joined by Northern Ireland's top-ranked player Josh Rock and Dutch prospect Wessel Nijman.
Jonny Clayton, Danny Noppert, Chris Dobey and Damon Heta also feature across Saturday's afternoon session, rounding out a field packed with major winners and rising talents.
The tournament's group stage features 32 players split into eight groups of four, each competing in a round-robin format across the first four days.
The top two from every group will progress to the knockout rounds, which begin on Wednesday, November 12th, with the tournament reaching its finale on the 16th.
Grand Slam of Darts groups:
Group A
Luke Humphries (1)
Michael Smith
Nathan Aspinall
Alex Spellman
Group B
Chris Dobey (8)
Damon Heta
Martin Lukeman
Jurjen van der Velde
Group C
Stephen Bunting (4)
Martin Schindler
Alexis Toylo
Luke Woodhouse
Group D
James Wade (5)
Gerwyn Price
Stefan Bellmont
Ricky Evans
Group E
Luke Littler (2)
Daryl Gurney
Karel Sedlacek
Connor Scutt
Group F
Gian van Veen (7)
Josh Rock
Wessel Nijman
Lisa Ashton
Group G
Michael van Gerwen (3)
Gary Anderson
Beau Greaves
Niko Springer
Group H
Jonny Clayton (6)
Danny Noppert
Cam Crabtree
Lukas Wenig