Rice served in the Hawaiian House of Representatives from 1870–1872 and from 1882–1884, and in the Senate from 1886–1890. Rice helped to draw up the 1887 Constitution of the Kingdom of Hawaii (known as the "Bayonet Constitution") and was one of the 13 committeemen who forced King David Kalakaua to sign it. He was appointed the last of the Governors of Kauai in 1891 by Queen Liliʻuokalani, whom he later helped to overthrow and place under house arrest, participating in the overthrow of the Hawaiian monarchy in 1893. Rice then served his childhood friend Sanford B. Dole, son of his school-master, who was named President of the new Republic of Hawaii, in the Senate from 1895–1898.