More than 10,000 people packed Maracanazinho Arena for the indoor match on clay.
Coming off the ATP Finals title, the top-ranked Djokovic entertained fans by dancing and putting on a big wig to imitate the hairstyle of the 36-year-old Kuerten, a former No. 1 in the world in the early 2000s.
Djokovic joined Kuerten for the inauguration of a public court in the Rocinha shantytown on Friday, and will play football before a Brazilian league match on Sunday along with Serbian countryman Dejan Petkovic, who starred for several Brazilian clubs in the last decade. Former Brazil stars Romario, Bebeto and Zico are expected to participate.