Garcia missed the cut at the US PGA Championship last week to fall outside the automatic qualification zone for the Ryder Cup, but he has bounced back in North Carolina to take a one shot lead on 14-under 196 at the Sedgefield Country Club.
The 32-year-old is one clear of American youngster Bud Cauley, who matched Garcia's 66 on Saturday, and South African Tim Clark who shot a 67 to also end the day on 197.
A first win on the PGA Tour in four years would guarantee Garcia's inclusion in the European side when the team is chosen in just over a week's time for the Sept. 28-30 matches.
"Winning is great. Winning means a lot no matter what. Obviously putting myself in a situation to win is already a good achievement but winning, no matter what it is, it's great," Garcia told reporters.
"Eighteen pars are not going to win it. 14-under par is not going to win it. You have to make some birdies out there. We'll see."
World number nine Jason Dufner fired the round of the day, a 63, to rocket up into a tie for fourth at 198 alongside fellow American Harris English (68) and former champion Carl Pettersson (68) of Sweden.
American Ryder Cup captain Davis Love III (66) is among three players in a tie for seventh at 199 while defending champion Webb Simpson is still in the mix at 10-under despite poor putting leading to a disappointing one-over 71.
"I got to figure out a way to get it done tomorrow," Simpson, the current U.S. Open champion, told reporters.
"I got to figure out a way to score and make putts. The birdies make the bogies disappear."
But they are all chasing Garcia, whose last win on Tour was at the 2008 Players Championship.
The Spaniard, who won twice on the European Tour last year, birdied the third and fifth holes with neat six-foot putts to get his round started and then nailed back-to-back birdies on the 12th and 13th to make a significant move.
His approach to the par three 12th was sublime leaving an easy short putt, however, he needed to negotiate 29-feet of green to pick up a shot a hole later.
A short par putt missed on the 14th threatened to stall his charge but he bounced back from the bogey with another birdie on 15, this time with a brilliant up and down from the sand, to go top.
"I've managed to hit a good amount of fairways which is important, a good amount of greens, too," Garcia said.
"The ones that I missed I've got up and down almost every time, which is great and, you know, just the last couple of days I managed to roll a couple putts at the right moment. So overall it's been quite consistent."
Clark wasted good chances to overhaul Garcia when he missed a short par putt on the 12th and two short birdie efforts on the 15th and 16th.