Charles Emory Smith grew up in upstate New York, graduating from the Albany Academy in 1858 and later from Union College in 1861. With the outbreak of the Civil War, Smith used his writing talents to serve as the military secretary to Brigadier General John Rathbone; he was later promoted to a role in the office of the adjutant general of the Army. Having long been a Republican, Smith first became associate editor and then editor, in 1874, of the leading Republican newspaper for upstate New York: the Albany Evening Journal.

Smith would later become editor of the renowned Republican newspaper, the Philadelphia Press, a political instrument for Pennsylvania Republicans. He raised funds and assistance for victims of the Johnstown Flood in 1889, and used these skills to distribute famine relief funds and supplies overseas as U.S. Minister to Russia between 1890 and 1892.

Smith returned to the Press for six years until his appointment to postmaster general by his close friend President McKinley. Of his time as postmaster general, postal historian Gerald Cullinan noted that Smith "was an effective politician but a miserable administrator," finding that under his tenure, "corruption ran riot in the Post Office Department." Charles Emory Smith would serve until the end of McKinley's presidency, dying in January of 1908.