Littlefield was born in Scituate, Providence County, Rhode Island, on April 12, 1829.[1] In 1831, his family moved to Warwick, Rhode Island, where he attended the common schools. He worked at a dry goods store in Central Falls, Rhode Island, before working at the Littlefield Manufacturing Company. He became a partner in the company, eventually serving as president.[2] He helped found the Pawtucket Hair Cloth Company in 1861 with his brother Daniel, and served as director until his death.[3]
In 1864, he served as the division inspector of the Rhode Island Militia, and was promoted to colonel. He served in the militia for five years.[4]
He was elected as Republican candidate to the governor's office, serving as the 35th Governor of Rhode Island from May 25, 1880, to May 29, 1883.[7] He succeeded fellow Republican Charles C. Van Zandt, who did not run for re-election in 1880. Littlefield beat the Democratic candidate Horace A. Kimball by 10,224 votes against 7,440, with 5,047 votes going to the Prohibition candidate Albert C. Howard. Republican Henry H. Fay became Lieutenant Governor.[8]
During his administration, the boundary line between Rhode Island and Massachusetts was established. He was succeeded May 29, 1883, by fellow Republican Augustus O. Bourn.
After leaving the governorship. Littlefield returned to his business interests. He was president of the First National Bank of Pawtucket, the Pawtucket Gas Company and the Pawtucket Street Railway in Pawtucket.[9]
Littlefield was the son of John and Deborah (Himes) Littlefield.[12] On February 9, 1853, Littlefield married Rebecca Jane Northrup. They had four children: Ebenezer N. Littlefield, Minnie J. Littlefield, George H. Littlefield and Alfred H. Littlefield.[13]