Wolff, a former Formula Ford driver who won the Dubai 24-hour race in 2006, will assist team principal Sir Frank Williams in his new role.
He has been involved with the Oxfordshire-based team as a shareholder and non-executive director since 2009.
"I am really looking forward to being able to take my responsibilities to a new level," said Wolff, 40.
Wolff's Scottish wife Susie was signed up by Williams as a development driver in April.
The Williams team, whose last Formula 1 champion was Jacques Villeneuve in 1997, gained their first Grand Prix victory in eight years earlier this season when Pastor Maldonado won in Spain.
Maldonado is 11th in this season's drivers' championship, with team-mate Bruno Senna 16th. The team are seven in the constructors' championship.
Team principal Williams said: "Toto's new role is about Williams looking forward and managing the successful running of the company."
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