Rio de Janeiro (Brazil) is 3.2 times larger than Puerto Rico.
Area: 13,790 km2 World Factbook
Population: 3,620,897 (July 2014) World Factbook
Puerto Rico, officially the Commonwealth of Puerto Rico, is an unincorporated territory of the United States, located in the northeastern Caribbean east of the Dominican Republic and west of both the United States Virgin Islands and the British Virgin Islands. Wikipedia
Rio de Janeiro is one of the 27 states of Brazil. It has the third largest economy of Brazil, with the largest being that of the state of São Paulo, and the second being that of Minas Gerais. The state of Rio de Janeiro is located within the Brazilian geopolitical region classified as the Southeast. Wikipedia