The Labour remainer will discuss Brexit progress as part of his role of chairman of the House of Commons Brexit Committee.
The cross-party group will also meet the European Parliament’s arch-federalist Brexit coordinator Guy Verhofstadt, and the chair of its constitutional affairs committee Danuta Hübner.
Former Shadow Foreign Secretary Mr Benn will attend alongside Labour’s Stephen Kinnock and Seema Malholda, Conservative MPs Stephen Crabb and John Whittingdale, Lib Dem Wera Hothouse and the SNP’s Joanna Cherry.
Leading Brexiteers Jacob Rees-Mogg and Peter Bone, however, will not attend talks with Mr Barnier.
Mr Rees-Mogg’s office confirmed he would not attend due to a number of long-standing speaking engagements.
It comes as Brexit talks are expected to accelerate from December, pushing forward to trade negotiations as Theresa May and David Davis make overtures to EU leaders.
Britain this morning announced a new “streamlined” registration system EU nationals will use to apply for permanent residency after Brexit in a bid to break the divorce talks deadlock.
The UK is offering all European citizens in the country before Brexit day the opportunity to apply for “settled status” which will grant them permanent residency and enshrine their rights in British law.