Matfield led the Barbarians to victory over New Zealand in 2009 and for his second appearance he will have South Africa team-mate Bakkies Botha alongside him at lock.
"My sights are firmly set on a successful Rugby World Cup campaign with South Africa in New Zealand but after that there is no better way to sign off in the northern hemisphere than another game for the Barbarians against international opposition at Twickenham," Matfield said.
Wales centre Roberts will be joined in a strong back division by compatriot Stephen Jones who, like Cipriani, will be making his Baa-baas debut, plus All Black Sonny Bill Williams and former Wallabies captain Stirling Mortlock.
Already confirmed to join Matfield and Botha among the forwards are Wales number eight Ryan Jones and New Zealand hooker Keven Mealamu.
Barbarians chairman John Spencer said: "Our annual autumn matches against South Africa, New Zealand and, this November, Australia are a major attraction in the calendar and that is particularly the case this year with no other pre-Christmas international at Twickenham.
"Player recruitment is going very well and we are confident that the final 22 will feature many more big names that will be making headlines in New Zealand in the next few weeks."
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