The Williams driver finished an impressive 15th-fastest and only a fraction of a second slower than the Mexican, who claimed before the British Grand Prix two weeks ago that he would not like to be beaten by a woman. Wolff became the first female to take part in a grand prix weekend in 22 years at Silverstone but her involvement was cut short by an engine problem.
However, she completed 22 laps at Hockenheim yesterday, producing a fastest time of 1:20.769 compared to Perez's 1:20.598. Wolff was also only 0.227sec behind her team-mate Filipe Massa in 11th and voiced her determination to reach the next level.
The Scot again suffered from technical troubles, this time a sensor problem on her opening lap out of the garage, but said: "I knew it was going to be our day and so I stayed calm and got the car back to the garage.
"I will be continuing my work in the simulator for the remainder of the season but I will be looking for the next opportunity to get behind the wheel as I really want to do more.
"The next step is obviously to do more and that's the difficult part, to get more opportunities. I was incredibly lucky to get the chance with this team this season and of course I have to try to get more opportunities. As we know that's not easy, so I need to start fighting for that now."
Nico Rosberg led a Mercedes one-two after FP1 but Lewis Hamilton turned the tables in the afternoon. In temperatures of 32C, the Briton finished just 0.024 seconds clear of his team-mate with a time of 1:18.341. However, Red Bull's Daniel Ricciardo could yet wreck Mercedes' hopes of a home victory. The Australian was only one-tenth of a second slower than Rosberg in third.