The Briton pulled out a stunning final flying lap in Saturday's qualifying at the Hungaroring to surprise Ferrari favourites Carlos Sainz (27) and Charles Leclerc (24) to take the top slot.
Red Bull's world championship leader Max Verstappen (24) will line up 10th.
"I think if we can maintain the position at the start, and be first coming out of the first lap and drive a solid race and have some good stops, why not? We can win this," Wolff told Sky Sports television.
"We haven't been in the hunt for wins this season, we know how quick Ferrari was all the time, Charles was solid in the lead in the last race," added the Austrian.
"Max is a bit further behind which is also not bad for an end result."
Mercedes have struggled this season after winning eight constructors' titles in a row and have had a roller-coaster ride with signs of improvement followed by disappointment and success coming after setbacks.
In Friday practice, the talk was of a tough weekend ahead after Russell was only eighth and seven-times world champion Lewis Hamilton (37) 11th in the second session.
Hamilton qualified seventh after problems with his car's drag reduction system.
Russell, in his first full season at Mercedes after three years at lowly Williams, was certainly not about to get ahead of himself.
"You don’t even think about it," he said when asked if he could imagine what the win would feel like.
"You take each day at a time. You don’t want to get carried away with yourself. You just focus step-by-step. Getting off the line, a good start, good first stint. Is it going to be a one, two, or a three stop?
"We know we have relatively speaking a faster race car than we do a qualifying car. If that’s going to be the case again this weekend, I’ll be very shocked. We just absolutely nailed to 100% and got every last millisecond out of it."
