The eighth of ten children of Taylor Duke (c. 1770 – 1830) and Dicey Jones (born c. 1780), Washington worked as a tenant farmer until he married Mary Caroline Clinton (1825–1847) in 1842.

Duke, aware that he would soon be called into military service, held a sale at his home on October 20, 1863, to sell the entirety of his farm equipment.

[3] He enlisted in the Confederate navy, and served in Charleston, South Carolina, and Richmond, Virginia, until his capture by Union forces in April 1865.

After a brief stint in a Federal prison, he was paroled and was sent by ship to New Bern, North Carolina, and from there, walked 134 miles (216 km) back to his homestead.

He and his sons built a factory on Main Street, and Washington spent the rest of the decade as a traveling salesman for Pro Bono Publico.

In 1880, at the age of 60, Washington Duke sold his share in the business to Richard Harvey Wright, a farmer from nearby Franklin County.

After selling his share in the company, Washington Duke became more involved with local politics as a member of the Republican Party, and devoted more time to charitable and philanthropic works.

[8] In 1896 while Trinity College was struggling financially, Duke donated $100,000 to the institution on the condition that it "open its doors to women, placing them on equal footing with men.