Portugal (Overseas Territories) is 2.1 times larger than Rio de Janeiro (Brazil).
Area: 92,090 km2 World Factbook
Population: 10,813,834 (July 2014) World Factbook
Portugal, officially the Portuguese Republic, is a unitary semi-presidential republic. It is located in South-Western Europe, on the Iberian Peninsula, and it is the westernmost country of mainland Europe, being bordered by the Atlantic Ocean to the west and south and by Spain to the north and east. 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