This handed a shock defeat to China's Olympic champions Cao Yuan and Zhang Yanquan in the 10m men's synchronized platform final.
Sascha Klein and Patrick Hausding claimed victory with 461.46 points from Russia's Victor Minibaev and Artem Chesakov second on 445.96 as Chinese teenagers Cao and Zhang came third with 445.56.
"It's an awesome sensation to be world champions," said an elated Hausding, who hails from Berlin, after the pair's success.
"I dreamt all my life with this moment, and we finally achieved it.
"That is something that nobody can take from us. Throughout the final, we had very positive feelings and things went well until the final dive.
"This is a great motivation to continue until the next Olympic Games in 2016 in Rio."
Head coach Lutz Buschkow described it as "a special day for German swimming".
This is only the third time China have failed to win the men's 10m synchro title since it was introduced at the 1998 world championships.
Cao, 18, and Zhang, 19, had led as favourites going into the fourth of the six rounds, but a rare mistake saw the pair drop to third.
Klein and Hausding, the newly-crowned European champions and silver medallists behind China at the 2011 world championships in Shanghai, hit the front in the fifth round and held their nerve in the final series.
The Chinese pair outscored the Germans on that last dive -- 99.36 to 96.12 -- but it was only enough to lift them to the third.
"What matters more is that we came to Barcelona very well prepared, both from a physical and a technical point of view," said Cao.
"We did our best and were ready for this competition."
China's Wu Minxia and Shi Tingmao had won the opening women's 3m synchronized springboard on Saturday, the opening day of the world championships.