France's Benoit Paire celebrates after winning his match against Spain's Pablo Carreno Busta.
Pouille had played in three finals in February and March but he lost the ground after that, although he should be among two singles players.
Defending champion France is one win away from back-to-back Davis Cup final berths after Lucas Pouille defeated Spain's Roberto Bautista-Agut 3-6, 7-6 (7-5), 6-4, 2-6, 6-4 to give his side a 2-0 lead.
They captured their one break point to seal the second and after repelling a fightback from the Spaniards, who held a 4-1 lead in the third, the French duo won on their third match point as Benneteau's brilliant backhand service return sealed the rubber and the tie.
Paire had never been selected for his country in the "World Cup of tennis" before, admitting himself that his explosive, erratic performances on court meant he could previously never properly be trusted.
Yet he has grown into a much more reliable and consistent performer in 2018 which prompted the champions' captain Yannick Noah to select him for his first tie at the unlikely age of 29 and he was rewarded with a virtuoso performance against a doughty opponent.
"I've waited a long time for this", said smiled Paire, the world number 54 who showed no signs of the hot-headed streak that cost him a $16,500 fine for an epic three-smashed-racket meltdown in Washington last month. "Though it's been a long time, hopefully it's not too late for me and I'll get more chances".
As Pouille was starting his match Croatia had already notched up their commanding 2-0 lead over the United Status in the other semi-final in Zadar.
France's Benoit Paire reacts during his match against Spain's Pablo Carreno Busta.
Bautista-Agut responded well, however, to win the fourth set, earning breaks of serve in the fourth and eighth games to force a decider.
His 87 unforced errors only complicated his task but he never relented and his persistency prevailed.
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