Leander was the son of William Calfee and Evalina S. Howard. He married Sarah Ella Martin.

Leander enlisted as a Confederate private on September 9, 1861. He was a farmer, aged 32, and served in Co. F, 54th Virginia Regiment. On January 1, 1862, he was noted as being sick. He was hospitalized on January 25, 1864 and then became a prisoner of war in Bentonville, North Carolina. Leander was confined the next day at Point Lookout, Maryland and returned home the following June.

He became a farmer, merchant and the postmaster in Pulaski, Virginia. With his brother Gustavus, they had the first store, a general store called "Calfee Brothers." Later there was the "L.S. Calfee and Company." In 1880, he obtained the contract for hauling zinc from the mines to Bertha Zinc Works, until 1885 when the railroads came into the area.

Article from "South-West Virginia and the Valley," by A.D. Smith, 1892:

"It is to him that the town of Pulaski owes much of its present prosperity, and, in fact, it is to him that it is indebted for its real business existence. He is a man of great and unusual versatility, and possesses the genius of being able to fill varied positions with equal ability and efficiency. He is a member of the City Council, wherein he finds opportunity to serve the city with constant and practical devotion."

Leander Sanders Calfee was a "Capitalist, merchant, banker (President of Pulaski Loan and Trust Co.), Mayor of Pulaski, farmer, principal shareholder in the Dora Furnace and Pulaski Development Company." He was a Republican in politics and a candidate for the House of Delegates.

The Pulaski Graded School for black students changed its name to Calfee Training School in 1921 in honor of Lee Calfee who had donated the land for the school.

The bridge that passes over New River on Highway 100 near Barren Springs, Wythe Co., Virginia is the Leander Sanders Memorial Bridge.