Gonzalez got the start over Tanner Roark, opposite Cubs' Kyle Hendricks at Nationals Park. The Nationals have Max Scherzer available in the bullpen as they try to win their first playoff series in four attempts since moving in 2005 to Washington, D.C.
Nationals manager Dusty Baker before the game said Scherzer could go for two innings and Roark would be "the early option" should he be needed.
"We weighed it out, right-left, and who's been, you know, the best behind the other two guys, but everybody is on call. And you know, Gio had gone Game 5 a couple years, three years ago, you know, and didn't do too well, so I'm sure redemption is on his mind, as well. All those factors went into choosing today's starter," Baker said.
Gonzalez pitched Game 2 against the Cubs, getting a no-decision in the Nationals' 6-3 victory. In that game, Gonzalez went five innings, giving up three runs on three hits -- two home runs -- and two walks. He struck out six.
Hendricks got the start for the World Series champions after throwing seven sharp innings in a 3-0 victory over Strasburg in Game 1. The Cubs are 4-2 in games started by Hendricks over the last two postseasons, with both losses by a 1-0 score.
The winner of Thursday's game will face the Los Angeles Dodgers in the NLCS.
ESPN Stats & Information and The Associated Press contributed to this report.