An historian, journalist and outspoken democrat, Philippe volunteered to serve as a Union Army officer in the American Civil War along with his younger brother, Prince Robert, Duke of Chartres. He was appointed as an assistant adjutant general with the rank of captain on 24 September 1861 and served under the name of Philippe d' Orléans, the Count of Paris. He served on the staff of the commander of the Army of the Potomac, Major General George McClellan, for nearly a year. He distinguished himself during the unsuccessful Peninsular Campaign. He resigned from the Union Army, along with his brother, on 15 July 1862. Philippe's history of the Civil War is considered a standard reference work on the subject.