The double-header on Sunday comes the day after three more Welshmen do battle in the Gallagher Premiership final at the same venue.
Liam Williams will be hoping to add to the Heineken Champions Cup medal he won with Saracens three weeks ago, while opposing him will be Alex Cuthbert and Tomas Francis in the Exeter Chiefs side.
The England XV side to face the Baa-Baas contains the former Cardiff Metropolitan University and Wales Under-20 second row Alex Dombrandt, ex-Wales Under-20 squad member Callum Sheedy, and former Wales Under-16 centre Johnny Williams.
The Baa-Baas will have Toulon scrum-half Rhys Webb on the field and Dragons No 9 Rhodri Williams ready to replace him.
Former Wales and British & Irish Lions hooker Richard Hibbard packs down in the front row with Joe Marler and John Afoa.
Wales wonder wing Jasmine Joyce will be hoping to follow up her stunning four-try salvo against the USA with another match-winning performance against the English women.
She is joined in the Baa-Baas back division by Welsh outside half Elinor Snowsill who is a vice captain of the side.
Barbarians: Charles Piutau (Bristol Bears / New Zealand); Niyi Adeolokun (Connacht / Ireland), Malakai Fekitoa (Toulon / New Zealand), Mark Atkinson (Gloucester), Taqele Naiyaravoro (Northampton Saints / Australia); Colin Slade (Pau / New Zealand), Rhys Webb (Toulon / Wales); Joe Marler (Harlequins / England), Richard Hibbard (Dragons / Wales), John Afoa (Bristol Bears / New Zealand), James Horwill (Harlequins / Australia, captain), Chris Vui (Bristol Bears / Samoa), Steven Luatua (Bristol Bears / New Zealand), Francois Louw (Bath / South Africa), Viliame Mata (Edinburgh / Fiji)
Reps: David Heffernan (Connacht / Ireland), Pierre Schoeman (Edinburgh), Finlay Bealham (Connacht / Ireland), Facundo Isa (Toulon / Argentina), Liam Messam (Toulon / New Zealand), Rhodri Williams (Dragons / Wales), Brock James (Bordeaux Begles), Filipo Nakosi (Toulon)
Barbarians Women: Danielle Waterman (Wasps / England); Jaz Joyce (Worcester Valkyries / Wales), Emily Wood (Gloucester Hartpury / England), Sene Naoupu (Old Belvedere / Ireland), Tova Derk (Wasps); Elinor Snowsill (Bristol Bears / Wales), Kristina Sue (Manawatu Cyclones / New Zealand); Rochelle Clark (Wasps / England), Fiao’o Fa’amausili (Auckland Marist / New Zealand), Steph Te Ohaere-Fox (Christchurch / New Zealand), Carmen Farmer (Glendale & USA), Dalena Dennison (Warringah & Australia), Justine Lavea (Ardmore Marist & New Zealand), Claire Malloy (Wasps & Ireland), Linda Itunu (Ponsonby / New Zealand, captain)
Reps: Heather Kerr (Darlington MP / England), Laura Keates (Worcester Valkyries / England), Gaelle Mignot (Montpellier / France), Tamara Taylor (Darlington MP / England), Georgina Gulliver (Saracens / England), Hannah Casey (Saracens / Ireland), Ceri Large (Gloucester Hartpury / England), Kayla Ahki (Unattached)