Six days after opening the preseason at home, the Cavs will meet the Heat on Oct. 11 in Rio de Janeiro. James and Cleveland open Oct. 5 against Maccabi Tel Aviv, the Israeli club formerly led by new Cavs coach David Blatt.
Miami won two NBA titles and reached the Finals in all four of James' seasons with the Heat. He returned to his first NBA team last month, signing with Cleveland for two years and $42.1 million -- along with the option to enter free agency again next summer.
The exhibition in Rio is part of the league's Global Games and allows Cleveland's Anderson Varejao his first chance to play in an NBA game in his native country.
The Cavs will also play in Cincinnati on Oct. 15 against the Pacers and against the Bulls on Oct. 20 on Ohio State's campus in Columbus. The NBA has visited South America only one other time, when the Bulls defeated the Wizards in a preseason game in Rio last October.
Information from The Associated Press is included in this report.