A native Hawaiian named Opukahaia, orphaned by the islands' wars, traveled to New England in 1809 (there is a monument to him in Punaluʻu) and learned to speak English.

In 1818 his stories (along with a few other companions) about the islands convinced the American Board of Commissioners for Foreign Missions to send a company to Hawaii.

Thurston and Hiram Bingham I, with whom he was ordained, were selected as leaders of the group which included a farmer, physician, three teachers, and a few native Hawaiian assistants.

They set sail a few weeks later on October 23, 1819, from Boston for a five-month voyage on the small merchant ship Thaddeus.

[1] Together with the group of the missionaries, that consisted of Hiram Bingham and others, Asa Thurston translated in 1832-1839 the Christian Bible into Hawaiian, Ka Baibala Hemolele.

Their second daughter Lucy Goodale Thurston (1823–1841) came to New England to obtain a higher education but died from pneumonia soon after their arrival to New York.

Their fifth child, Thomas Gairdner Thurston graduated from Yale in 1862, studied theology, and returned to Hawaii, where he preached until the time of his death in 1884.