The first part of the railroad was constructed in 1853, reaching Leesburg by 1858. At one point it was called the Washington and Ohio Railroad and had intentions to extend to the Ohio River at Parkersburg, WV. It only made it as far as Bluemont, VA in 1900. It came under the control of the Southern Railway in 1894, and then the Washington and Old Dominion bought the Alexandria-to-Purcellville section from Southern in 1945. The Chesapeake and Ohio Railroad bought the W&OD in 1956 and owned it until abandonment.
The W&OD ceased operation on August 27, 1968, its last major business being the hauling of material for the construction of Dulles Airport and the community of Reston. The rails were removed soon after this.
The line went from Alexandria (at the Potomac Rail Yard) to:
- Arlinco
- Barcroft
- Bluemont Junction
- Falls Church
- Dunn Loring
- Wedderburn
- Vienna
- Hunter
- Sunset Hills
- Herndon
- Sterling
- Ashburn
- Trap Rock
- Leesburg
- Paeonian Springs
- Hamilton
- Ivandale
- Purcellville
- Round Hill
- Bluemont
At one point there was a branch from Bluemont Junction to Lacey, Douglas, and Rosslyn.
The right-of-way has been converted into a walking/hiking trail from Alexandria to Purcellville.