It is a big step for the 31-year-old Scot, who replaces Williams' Finnish regular Valtteri Bottas for first practice at the British Grand Prix, and a day she has been working towards for years.
The 90-minute session will be the closest she has come to ending what is now a 38-year wait for a woman to actually race with the men but it could also be as far as she gets in that ambition.
There are no plans for a race drive but Wolff aims to show at least that the only barriers for women aspiring to enter the sport should be the same as for the men - the metal ones ringing the circuit.
"I think tomorrow is a really big day for Susie," deputy team principal Claire Williams, daughter of founder Frank, told reporters.
"She goes out there with her peers in a competitive situation. Yes we are doing a lot of setup work over long runs with heavy fuel loads and stuff but I still think you will be able to judge her more than you have been able to in the past."
Wolff, wife of Mercedes motorsport head Toto who is also a Williams shareholder, made her test debut for the team at Silverstone last year.
She will be working through the same programme Bottas - who finished third at the previous race in Austria - would have carried out.
PROVIDING FEEDBACK
That means preparing the car for the second and third practice sessions and Saturday qualifying and providing feedback for engineers.
"She's got to deliver technically, which she's done," Williams said.
"If she hadn't have done that we wouldn't have allowed her to progress up into the test driver role last year and then the Friday sessions this year.
"We're not running her tomorrow to see how good she is," added Williams.
Fellow drivers welcomed her involvement.
Lewis Hamilton, the 2008 world champion who is a race favourite for Mercedes in his home grand prix, said Wolff was one of the few women he could recall competing against in junior series.
"We raced Formula Renault together. She was great. We shared a podium together a couple of times. I think she’s done remarkably well in her career," said the Briton.
"It’s going to be really cool, I think, to see her in a Formula One car tomorrow."
Italian Lella Lombardi, in 1976, was the last woman to race in Formula One. The last to take part in any stage of a grand prix weekend was Italian Giovanna Amati who tried and failed to qualify with Brabham in 1992.
(Editing by Tony Jimenez)
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