Accompanied by a 15-member business delegation, he will address an industry event to boost economic ties with the mineral-rich nation.
Indian private companies are interested in having a stake in Liberia's mineral resources of iron ore, gold, diamonds and copper, as well as in its plantations of rubber, coffee and cocoa.
From Liberia, Tharoor will head to Ghana from Sep 19 to 21, primarily as a special representative of the Indian prime minister at the birth centenary celebrations of the West African country's first president Kwame Nkrumah, who was one of the founders of NAM along with Jawaharlal Nehru.
India had been asked to send a high-level participant by Ghanaian President John Evans Atta Mills, who had sent a personal request through a special envoy to Indian Prime Minister Manmohan Singh.