Saab indicated more releases would follow. "The cycle does not close today," he said.
Ramon Guevara, one of several opposition leaders who attended the ceremony as "guarantors" of the prisoners, said Rodriguez had told him that prominent opposition figure Villca Fernandez would be released today.
Fernandez, 34, was arrested in January 2016 on charges of "incitement to hatred" and disseminating false information.
Guevara, governor of western Merida state, said Rodriguez had given a commitment that Fernandez - a member of opposition leader Leopoldo Lopez's party -- was to be handed over at Caracas airport and immediately taken to Merida state today.
Maduro had requested the releases "for the sake of national dialogue and reconciliation," Rodriguez said.
Some 124 prisoners, including American Joshua Holt who was held on spying charges, have been released since June 1.
Under Maduro, Venezuela is going through the worst economic crisis in its history.
Upon his re-election on May 20, Maduro promised to work for reconciliation and offered to free political opponents who have not committed serious crimes, in order to "overcome the wounds" of the protests against him, which have left some 200 dead since 2014.