The pope arrived in Rio de Janeiro on Monday for the run-up to World Youth Day.
Before meeting with the bishops, he presided over Mass at Rio de Janeiro's Cathedral and then met with politicians and leaders of Brazilian society at the Municipal Theater.
The unpredictable pontiff even placed an indigenous headdress on his head briefly during the encounter.
Friday night, an estimated 1.5 million people turned out and the pope lead them in prayer.
Presidents and heads of state from across Latin America were scheduled to attend the final Mass, at which the pope is scheduled to announce the location of World Youth Day 2015.