France, Sweden and Argentina joined in the rush to victory, with all three needing just a Saturday doubles rubber win to cement a spot in the July quarter-finals.
The 2009 champion Spain raced away with a pair of rapid-fire singles wins indoors, as Fernando Verdasco, substituted for the injured David Ferrer, defeated Xavier Malisse 6-4, 6-3, 6-1.
Ferrer, who beat Nadal at the Australian Open, was forced out with an inflamed shoulder nerve.
"The beginning of the match was the key. You get the confidence," Verdasco said.
World number one Nadal then blasted young hope Ruben Bemelmans 6- 2, 6-4, 6-2 to establish Spanish superiority at the close of day one.
Both men won in less than two hours, in a tie where the winner faces either the US or Chile in the quarter-finals.
"(Bemelmans) is the kind of player who is a bit tricky when I'm coming back from injury," said Nadal. "I was serving well and felt comfortable. It was a good match throughout."
Spain are bidding for a fifth trophy after winning their first round in the space of a decade ending in 2009.
In an airplane hangar at Vienna airport, losing 2010 finalist France took flight as a team of substitutes rose to the occasion to give the visitors the 2-0 edge.
Unfancied number 55 Jeremy Chardy began the afternoon over top Austrian Jurgen Melzer 7-5, 6-4, 7-5 with 14 aces, while Gilles Simon delivered a second blow as he beat Stefan Koubek 6-0, 6-2, 6-3.
France, 7-0 over Austria, are missing three main hopes due to injury as Gael Monfils, Jo-Wilfried Tsonga and Richard Gasquet sit out the competition.
"I played very good today. I'm happy for me and the team," said Chardy, a loser of every set he had played so far this season, with his last ATP victory collected four months ago.
Chardy substituted for Gasquet, out with a shoulder injury.
"Guy (Forget, the French captain,) gave me the right tactics, I just had to stay focused. I stayed aggressive against Jurgen," Chardy said.
Sweden hammered Russia, with Robin Soderling beating Igor Andreev 6-3, 6-3, 6-1 and Joachim Johansson making a successful comeback to the sport with his defeat of Teymuraz Gabashvili 6-3, 7-6 (7-4), 6-4.
In Buenos Aires, Argentine iron man David Nalbandian played with the pain of a hernia to defeat Romanian Adrian Ungur and give the host nation a 1-0 lead.
Juan Monaco sealed the 2-0 margin over Victor Hanescu 7-6 (7-5), 1-6, 6-1, 6-1.
Andy Roddick got the US off to a solid start in Santiago, defeating Nicolas Massu 6-2, 4-6, 6-3, 6-4.
But Wimbledon marathon man John Isner went down for a 1-1 day as Paul Capdeville spent four and a quarter hours in beating the big hitter 6-7 (5-7), 6-7 (2-7), 7-6 (7-3), 7-6 (7-5), 6-4.
Wimbledon finalist Tomas Berdych of Czech Republic trailed in the first set but hung on to beat Mikhail Kukushkin of Kazakhstan 7-6 (7-5), 6-2, 6-3 for a 1-1 score, after Kazak Andrey Golubev beat Czech Jan Hajek 7-6 (7-4), 6-7 (3-7), 1-6, 7-6 (7-4), 6-3.