Ralf Schumacher established Williams as German Grand Prix favourites after eclipsing his older brother Michael in Friday's first qualifying.
While Ralf stood out on a dominant afternoon for his BMW-powered team, Ferrari's Formula One leader struggled to hold his own and was more than a second off the pace in ninth position.
McLaren's Kimi Raikkonen, seven points behind the Ferrari driver in the standings, was sixth quickest on a hot day that clearly played into the hands of Michelin-tyred teams over Bridgestone's runners.
Colombian Juan Pablo Montoya, Ralf's team mate, was second with Michelin cars filling the top seven slots.
Italian Jarno Trulli was third for Renault, Australian Mark Webber fourth in a Jaguar and Spaniard Fernando Alonso fifth for Renault.
Briton Justin Wilson, who switched from Minardi to Jaguar last week, was seventh -- rocketing from his regular place at the back of the grid to record a quicker lap than either Ferrari.
"The car was perfect, brilliantly balanced," said Ralf, who won at Hockenheim in 2001. "The tyres were very good and we sorted out the small problems we had in the morning.
"I'm looking forward to the race. It's probably going to be hot and that suits our package."
Montoya was also satisfied: "The car has a good balance, we made the right tyre choice and we're well set for Saturday."
Minardi's Danish rookie Nicolas Kiesa endured a nightmare debut, failing to get out of the pit lane at the end of the session.
He will start first in Saturday's decisive qualifying, followed immediately by Canadian Jacques Villeneuve, who spun his BAR at turn one on his flying lap.