African Country by Size List. Africa Which are the top twenty largest, smallest, and territorial country in Africa by land area? 1. The continent of Africa is the world’s second largest based on land area and population just after Asia. 2. Top five largest countries of Africa are Algeria, Congo Democratic Republic of the, Sudan, Libya and Chad. 3. Top five smallest African countries and territories are Mauritius, São Tomé and Príncipe, Seychelles, Saint Helena and Mayotte. African Country from largest to smallest Area sq mile Area sq km Algeria 919,595 2,381,740 Democratic Republic of the Congo (DRC) 905,568 2,345,410 Sudan 718,723 1,861,484 Libya 679,362 1,759,540 Chad 495,755 1,284,000 Niger 489,191 1,267,000 Angola 481,354 1,246,700 Mali 478,767 1,240,000 South Africa 471,011 1,219,912 Ethiopia 435,186 1,127,127 Mauritania 397,95