Orlow W. Chapman was born in 1832, in Ellington, Connecticut, though he made his life's work and home in New York. While in Ellington, Chapman received his primary education in a local academy. He then proceeded to graduate from Union College of Schenectady, New York, in 1854. After earning his undergraduate degree, he spent two years as Professor of Languages in the Fergusonville Academy in Delaware County. Chapman then studied law under Robert Parker of Binghamton, New York. In 1856, he was admitted to the bar.
Following his admission to the bar, Chapman began his career as a politically active New Yorker and lawyer. He served as Binghamton District Attorney from 1862-1868. In 1870, Chapman was the Republican nominee and winner of the New York State Senator race for the 24th District, serving in this position until 1871. Subsequently, he was appointed Superintendent of New York Insurance Department, where he served until 1876. During Chapman's time as superintendent he also served as president of the National Insurance Commissioners' Association and he focused on eliminating corrupt states' fostering of large and fraudulent companies. During his term Chapman also initiated the creation of an Executive Committee formed from and elected by Insurance Superintendents from each state.
On May 29, 1889, President Harrison appointed Chapman Solicitor General of the United States. His service was cut short when Chapman died of pneumonia on January19, 1890, while working in Washington, D.C. Orlow W. Chapman was buried near his home in Binghamton, New York.