Williams, a silver medallist in the women’s 100m at the 2004 Athens Olympic Games and part of the 2012 gold-medal relay squad at London 2012, was the brakewoman on USA-1, piloted by Elana Meyers.
“The nerves definitely overtook me,” admitted Williams. “All day long, I've been nervous, well before we got here.”
“And I got on that line and I knew something good was going to happen because I was literally ready to jump out of my skin and that's a feeling I hadn't had in a while in track and field.
“It was good to have that feeling back and know what that means -- that means going fast.”
Meyers, who won a bronze medal at Vancouver 2010, executed two consistent runs to clock a combined time of 1 minute 54.89 seconds and finish 0.23 seconds ahead of reigning Olympic champions, Kaillie Humphries and Heather Moyse of Canada.
In her first run, two-time world champion Meyers set a new track record with a time of 57.26sec.
“It’s not over”
“It feels pretty good but we've got a lot of work to do,” Meyers said, recognising that the margin of their lead left no room for complacency going into the final two heats.
“It's not over. It's a battle. We're going to go back, get some food, get some sleep, rest up and be ready to go again.”
Meanwhile, the USA-2 team made up of Jamie Greubel and Aja Evans are third with a time of 1 minute 55.45 seconds.
The medal winners will be decided after the third and fourth runs on 19 February, with the times of all four runs added together to determine the winner.