The victor of the Spain-France tie will face either Croatia or the United States in the 2018 Davis Cup final.
Before almost 14,000 fans, Paire fired 16 aces and 37 winners, compared to his rival's one and eight, respectively. Find us on Facebook too!
After Paire had breezed to victory in less than two hours, French No.1 Pouille, back where he won the winning point for his country in last year's final, battled from a set down to beat Roberto Bautista Agut in a classic five-setter 3-6 7-6 (5) 6-4 2-6 6-4 in three hours 41 minutes.
"I've waited a long time for this and it's a dream to win on my debut", said Paire. Matches will be played on an indoor court at the 27,500-capacity Pierre Mauroy Stadium, with the roof closed.
His 87 unforced errors only complicated his task but he never relented and his persistency prevailed.
Feliciano Lopez and Marcel Granollers should play for the first time together in the Davis Cup, with Granollers making a return to the national team for the first time since 2013, playing with Marc Lopez and Tommy Robredo in the past.
Speaking after the match, Benneteau, who came out of retirement to play this doubles match, offered no assurances over his availability for the final later this year.
His win, with Paire doubling up, leaves France 2-0 and heading for a final against either Croatia or the United States in November.
Croatia's top player and world number six Marin Cilic then defeated Frances Tiafoe, a Davis Cup débutant 6-1, 6-3, 7-6 (7/5) to leave the hosts on the brink of the final.
Earlier Borna Coric gave Croatia a flying start by defeating Steve Johnson 6-4 7-6 (4) 6-3 in the opening rubber.
Jim Courier's team is missing two top players - John Isner, world number 10 who has stayed home due to family reasons, and injured Jack Sock.