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- Australia: The capital of Australia is Canberra, while the most populous city is Sydney.
- Brazil: The capital of Brazil is Brasília, while the most populous city is São Paulo.
- Canada: The capital of Canada is Ottawa, while the most populous city is Toronto.
- Chile: The capital of Chile is Santiago, while the most populous city is also Santiago.
- China: The capital of China is Beijing, while the most populous city is Shanghai.
- India: The capital of India is New Delhi, while the most populous city is Mumbai (formerly known as Bombay).
- Indonesia: The capital of Indonesia is Jakarta, which is also the most populous city.
- Japan: The capital of Japan is Tokyo, which is also the most populous city.
- Mexico: The capital of Mexico is Mexico City, which is also the most populous city.
- Nigeria: The capital of Nigeria is Abuja, while the most populous city is Lagos.
- Pakistan: The capital of Pakistan is Islamabad, while the most populous city is Karachi.
- Philippines: The capital of the Philippines is Manila, which is also the most populous city.
- Russia: The capital of Russia is Moscow, which is also the most populous city.
- South Africa: The capital of South Africa is Pretoria, while the most populous city is Johannesburg.
- United States: The capital of the United States is Washington, D.C., while the most populous city is New York City.
These are just a few examples, and there are other capitals around the world that are not the most populous cities in their respective countries or territories.