World number 10 Goffin was beaten 6-3 6-3 by local favourite Julien Benneteau, but Pouille's 7-6(6) 6-3 defeat by American Jack Sock gave Goffin the seventh place in the Nov. 12-19 tournament in London.
He joins world number one Rafa Nadal, six-times champion Roger Federer, Dominic Thiem, Marin Cilic and debutants Alexander Zverev and Grigor Dimitrov in the eight-man event.
The last spot is currently held by Spain's Pablo Carreno Busta but Juan Martin Del Potro, Roberto Bautista Agut, John Isner and Sock still have a chance to qualify depending on results in Paris.
(Reporting by Julien Pretot; Editing by Ed Osmond)
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