Although Smoltz and James will start the season on the disabled list, they are eligible to come off in time to face the Mets in the series finale.
"It looks like Smoltzie should be ready to go, but we're covered even if he isn't," Braves manager Bobby Cox said.
Smoltz, who made just one Grapefruit League start, is scheduled to pitch on Sunday in a Minor League game in Florida. The veteran right-hander has been bothered by tightness between his neck and right shoulder, but he said he felt better after a bullpen session on Thursday in Florida. Smoltz will throw two side sessions next week after returning from Florida.
James is recovering from a slight left rotator cuff tear. He threw two scoreless innings in a Grapefruit League game and has also pitched twice in Minor League games. The left-hander is scheduled to pitch on Tuesday in Rome, Ga., in a simulated game against the Braves' Class A South Atlantic League team.
Bennett made the opening roster as a spot starter and long reliever, beating out Buddy Carlyle. On Saturday, Carlyle was optioned to Triple-A Richmond as the Braves finalized their 25-man roster.
Atlanta will carry 12 pitchers, three catchers, six infielders and four outfielders. Infielder Omar Infante is on the 15-day disabled list along with Smoltz, James and reliever Mike Gonzalez.
The Braves won't need a fifth starter until April 6 because of an off-day on Tuesday.
Tim Hudson will pitch against the Nationals in Washington on Sunday night, with Tom Glavine starting the home opener on Monday night against Pittsburgh.
Jair Jurrjens will pitch against the Pirates on Wednesday, followed by Mike Hampton against Pittsburgh on Thursday. Hudson and Glavine will start the first two games of the weekend series against the Mets.
Blaine Boyer, Chris Resop and Royce Ring -- all out of options -- won spots in the bullpen. They join closer Rafael Soriano, Peter Moylan, Manny Acosta and Will Ohman. Ring and Ohman are left-handers.
Ruben Gotay, claimed off waivers from the Mets on Friday, joined the Braves on Saturday and played in the exhibition finale against Cleveland. The infielder was out of options.
"I was surprised," Gotay said. "I thought I played well last season. But I just have to come here and show what I can do. I want to help this team."
Gotay, a switch-hitter, batted .295 in 98 games with the Mets. He hit .288 (15-for-52) as a pinch-hitter.
"He can swing the bat," Cox said.
Guy Curtright is a contributor to MLB.com. This story was not subject to the approval of Major League Baseball or its clubs.