Charles H. Littlefield was born around 1836 in Coventry, Rhode Island, to Henry and Maria Littlefield. His father was a farm laborer. He grew up and attended school in Sterling, Connecticut, and he married Phebe Wells around 1858. They had at least four children: Edwin, born around 1866; William, born around 1871; Lillian, born around 1874; and Harriet, born around 1879.
He enlisted in the Union army on August 11, 1862, and he mustered in as a private in Company K of the 21st Connecticut Infantry. The regiment took part in the Battle of Fredericksburg, the Overland Campaign, the siege of Petersburg, and the Appomattox campaign. He was discharged for disability on February 11, 1865.
He returned to Sterling after the war, and he earned a living as a farm laborer. His wife died on March 16, 1907, and he died in Sterling on February 27, 1914.