The son of American Protestant missionaries, Dole spent two years in the United States (1866–68) studying at Williams College in Williamstown, Mass. He then returned to Hawaii, practiced law in Honolulu (1869–87), and was twice elected to the Hawaiian legislature (1884, 1886). An opponent of the policies of King Kalakaua, Dole was a leader of the reform movement that brought about the adoption of a constitution in 1887. Also in 1887, he was appointed a justice of the Supreme Court of Hawaii.

In January 1893 Dole agreed to serve as the leader of the committee, acting for Hawaiian sugar interests and their American allies, that was formed to overthrow Queen Liliuokalani (who had succeeded her brother, Kalakaua, in 1891) and to seek annexation of Hawaii by the United States. The committee deposed the queen and installed a provisional government with Dole as president (Jan. 17, 1893), but annexation was blocked when President Grover Cleveland withdrew an annexation treaty from the Senate and demanded the restoration of Liliuokalani to the throne. Refusing to recognize Cleveland's authority in the matter, Dole and his colleagues established the Republic of Hawaii (1894), with Dole as president, and continued to seek annexation. When, finally, in 1900 Congress created the Territory of Hawaii, Dole was appointed the first territorial governor by President William McKinley. In 1903 he resigned to become judge of the U.S. district court of Hawaii, a post he held until his retirement in 1915.