Born in Crittenden County, Kentucky, DeBoe attended Ewing College in Illinois, studying both law and medicine.
He graduated from the University of Louisville School of Medicine and practiced for a few years.
He was afterward elected as a Republican to the United States Senate and served from April 29, 1897, to March 3, 1903.
Ten years later he served as the postmaster of Marion, Kentucky from 1923 to 1927.
He died in Marion and was interred in Maple View Cemetery.