China's surprise defeat handed Olympic champion Cao Yuan and Zhang Yanquan in the men's synchronized 10m platform final.
Sascha Klein and Patrick Hausding claimed victory with 461.46 points from Russia's Victor Minibaev and Artem Chesakov second at 445.96 as Chinese teenager Cao and Zhang came third with 445.56.
"It's an amazing sensation to be a world champion," said an elated Hausding, who came from Berlin, after the pair's success.
"I dreamed of this moment all my life with, and we finally achieved it.
"That is something that nobody can take from us. Throughout the end, we had a very positive feeling and everything went well until the end of the dive.
"This is a great motivation to continue until the next Olympics in 2016 in Rio."
Lutz Buschkow head coach described it as "a special day for a swim Germany".
This is only the third time China has failed to win the men's 10m synchro title since its introduction in 1998 world championships.
Cao, 18, and Zhang, 19, has taken the lead as the favorite entered the fourth of six rounds, but errors rarely saw the pair slipped to third position.
Klein and Hausding, the newly-crowned European champion and silver medalist in 2011, China won the world championships in Shanghai, hit the front in the fifth round and held their nerve in the final series.
Chinese couples to surpass Germany in the last dive - 99.36 to 96.12 - but it was just enough to lift them to third.
"What is more important is that we come to Barcelona was very well prepared, both from a physical and technical point of view," said Cao.
"We do our best and be ready for this competition."
China's Wu Minxia and Shi Tingmao has won the open women's 3m synchronized springboard on Saturday, the opening day of the world championships.
