Zambrano, who has not pitched since Aug. 12 with the Cubs, was expected to pitch for Caribes in the Venezuelan Winter League.
The right-hander's season ended in Atlanta after he gave up five home runs in that game, then was ejected for throwing inside at Chipper Jones. Zambrano was placed on the 30-day restricted list. When he came off the list, the Cubs determined there wasn't enough time for him to get back in shape for the final few weeks of the season, and Zambrano never rejoined the team.
Zambrano finished 9-7 with a 4.82 ERA in 24 starts, totaling 145 2/3 innings with Chicago.
Caribes also lists Tigers pitcher Joel Zumaya, Marlins infielder Omar Infante and Pirates outfielder Jose Tabata on the roster. Former big leaguer Julio Franco is managing the team.
Whether Zambrano, 30, returns to the Cubs is still to be determined. In September, chairman Tom Ricketts said he had a hard time imagining the right-hander rejoining the team after his behavior this season.
Theo Epstein, the Cubs' new president of baseball operations, said Tuesday he wanted to talk to Zambrano before automatically dismissing the pitcher.
"I need to get to the bottom of that," Epstein said. "I think the best organizations get the most out of their players, even the ones that might be harder to get the most out of. But the best organizations also know when it's time to move on."
Zambrano is owed $19 million for next year and has a full no-trade clause.
"He's got talent," Epstein said. "Obviously, things haven't gone the way he would have liked or the organization would have liked the last few years."
Still to be resolved is the grievance filed by the Major League Baseball Players Association on Zambrano's behalf. The players union, Major League Baseball and the Cubs will process that this offseason.
Carrie Muskat is a reporter for MLB.com. She writes a blog, Muskat Ramblings, and you can follow her on Twitter@CarrieMuskat. This story was not subject to the approval of Major League Baseball or its clubs.