At the hill-top Montjuic pool with its spectacular views over the Catalan city, Chinese pair Cao Yuan and Zhang Yanquan unexpectedly had to settle for bronze behind Russian silver medallists Victor Minibaev and Artem Chesakov after fluffing their fourth dive.
Olympic champions in London last year, Cao and Zhang started brilliantly and seven of 11 judges awarded them the maximum 10 points for their second dive.
However, there was no way back after their horrible fourth effort and ultimately they were relieved to be on the podium.
It was only the third time China have failed to win the event since its introduction at the 1998 championships and was Germany's first victory.
Hausding and Klein, who were seventh at the London Olympics, scored 461.46 points from their six dives, with Minibaev and Chesakov amassing 445.95 and the Chinese 445.56.
"It's an awesome sensation to be world champion," an emotional Hausding, silver medallist at the 2008 Beijing Olympics, told reporters.
"A surprise? It wouldn't be fair to say that it wasn't a surprise ... we hope this is just the start of a great week," he added.
"I dreamt all my life of this moment and we finally achieved it. That is something that nobody can take away from us.
"This is a great motivation to continue until the next Olympic Games in 2016 in Rio."
(Writing by Iain Rogers in Madrid, editing by Alan Baldwin)
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