Slovakia's Filip Horansky stunned Italy's world number 21 Lorenzo Sonego 7-6(2), 6-3 to level their qualifying tie on Friday for a place in the Davis Cup Finals later this year.
The 12 winning teams from the home-and-away qualifiers on Friday and Saturday will join Croatia, who secured automatic qualification for the 2022 Finals as last year's finalists, and wild cards Serbia and Britain.
Russia's title defence is uncertain after governing body International Tennis Federation (ITF) suspended the memberships of Russia and Belarus and withdrew their entries from team competitions following the invasion of Ukraine.
The 29-year-old Horansky, ranked 203rd in the world, defeated Sonego in an hour 46 minutes in Bratislava to cancel out Jannik Sinner's hard-fought 6-4, 4-6, 6-4 win over Norbert Gombos earlier.
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"My feelings are amazing," Horansky said. "To play in front of the home crowd, to win such a tough game, it's the best feeling a player can have. I'm surprised how I played."
Playing for the first time since he was kicked out of the ATP event in Acapulco for smashing his racket repeatedly against the umpire's chair, world number three Alexander Zverev beat Brazil's Thiago Seyboth Wild 6-4, 6-2 to give Germany a 1-0 lead.
Germany failed to build on Zverev's win, however, with Thiago Monteiro recording a 6-3, 1-6, 6-3 win over Jan-Lennard Struff to make it all square in the tie.
Canada, who are without top-20 players Felix Auger-Aliassime and Denis Shapovalov, will require a stunning turnaround to win their tie against the Netherlands.
Botic Van de Zandschulp beat Alexis Galarneau 7-5, 7-6(9) to put the Netherlands in front before Tallon Griekspoor eased past Steven Diez 6-4 6-4 to give his country a commanding 2-0 lead.
Spain's Carlos Alcaraz impressed on his Davis Cup debut as he beat Marius Copil 6-4, 6-3 in Marbella to give his side, who are without 21-times major winner Rafa Nadal, a 2-0 lead over Romania heading into the final day.
The 18-year-old Alcaraz, who was ruled out of the Davis Cup Finals last year after testing positive for COVID-19, became the youngest player to clinch an ATP 500 title at last month's Rio Open and is having a breakthrough year on tour.
"I try not to put pressure on myself to be the future of Spanish tennis," Alcaraz said.
"Lots of people say to me, 'you're going to be number one, you're going to be the best'. But I try not to pay too much attention to it. I try to follow my own path."
The United States and France also put themselves in a comfortable position by taking a 2-0 lead over Colombia and Ecuador respectively in their home ties on the opening day.
Australia's tie against Hungary in Sydney is set for an exciting second day with world number 30 Alex de Minaur's victory cancelling out Marton Fucsovics' defeat of Thanasi Kokkinakis.
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