Driving an identical Williams-Mercedes to the Brazilian 11-time winner and 2008 world championship runner-up the Oban-born development driver out-paced him early on in first practice yesterday for Sun-day's German Grand Prix.
Wolff, 31, who hopes to be the first woman driver to race in Formula One in 22 years, left her team-mate briefly struggling in her wake, forcing him to try harder to finish one spot above her. She completed 22 laps, finishing 15th and a place above Mexican driver Sergio Perez, who earlier caused controversy with sexist remarks about her.
Two weeks ago at the British Grand Prix at Silverstone she barely completed a lap in practice but yesterday, not even two fines totalling £1,580 for pit lane speeding could spoil her day.
Wolff said: "It was a case of going for it and it all felt fantastic. I picked up fines, so an expensive morning!"
BBC pundit Allan McNish said: "To be that close to Massa was a very strong performance."