The Purcellville National Bank was founded in 1901 and began business on 2 January 1902 as the first bank established in western Loudoun. Mr. W.P. Pancoast (1852-1940) served as the organization's first president, Dr. G.E. Plaster (1826-1925) as its vice-president, and Mr. T.M. Fry (1868-1922) as its cashier. In addition, the bank had a board of thirteen directors.

The bank burned down during the fire of 8 November 1914, which destroyed most of the central business district of Purcellville, but its steel vault remained intact. A new, bigger building was erected in 1915. The bank did much to promote itself, advertising in the papers and sending out promotional booklets. On one occasion, the bank even purchased a herd of ewes, proposing to sell them cheaply to young men who were interested in raising sheep. In spite of the Great Depression, the town of Purcellville actually grew during the 1930s. The Purcellville National Bank closed on 6 March 1933 when the Federal Government declared a national Bank Holiday; it reopened on 15 March and did not close down again.

In 1959, banking organization J.R. Trammell & Co. purchased controlling interest in the Purcellville National Bank. In 1960, with the permission of the Federal Reserve Board, J.R. Trammell & Co. sold the controlling interest to First Virginia Bank, making the Purcellville National Bank the fourth bank under the First Virginia Corp. In 1964, directors of the Purcellville National Bank, Loudoun National Bank of Leesburg, and First Virginia Bank agreed to combine the Loudoun and Purcellville banks as the First National Bank of Loudoun County. The Federal Reserve Board did not grant permission, however, and instead the Purcellville National Bank changed its name to the First National Bank of Purcellville and expanded to have two new branches in Leesburg and Sterling. The bank finally closed or was bought out some time after the 1960s, but it is unclear when or by whom.