The former Labour and Respect MP and current vice-president of the Stop The War Coalition will feature on the segment of the show where a discussion is helmed by comedian David Mitchell.
He will be joined by columnist Hugo Rifkind, the son of former Conservative cabinet minister Malcolm Rifkind.
"@RealDMitchell will be joined by @georgegalloway and @hugorifkind on tonight's show #10oclocklive," the programme's official Twitter feed confirmed.
Galloway added on his own feed: "I am appearing v Murdoch columnist Hugo Rifkind on the Falklands issue tonight on C4's 10 o'clock Live. 10pm C4."
Former Labour Party strategist Alastair Campbell and Northampton Town defender Clark Carlisle discussed football with Mitchell on last week's show, the first in the second series.
Galloway starred in the 2006 edition of Celebrity Big Brother and famously impersonated a cat for actress Rula Lenska on the show.
The scene was last year named the 'Most Memorable Moment' of Celebrity Big Brother.
> This Week's Must-See TV: 5 Shows You Shouldn't Miss
Watch CBB4's Pussy George video below: