In 1871 Philippe returned with his parents to France. He was educated at home at the Château d'Eu and at the Collège Stanislas de Paris. In 1880 he received the title duc d'Orléans from his father. On June 16, 1881, he received the sacrament of confirmation at Eu.
Philippe finished his military education at the Royal Military Academy Sandhurst. He was attached for service to the King's Royal Rifle Corps which was then serving in India. He never had an actual commission in the British Army, since it was necessary to avoid the French law forbidding a Frenchman to hold a commission in a foreign army without the permission of the head of state. He took rank as a lieutenant and served in India from January 1888 to March 1889. He was a staff-officer to Lord Roberts, then Commander-in-Chief in India.
In October 1889 Philippe went to Switzerland to complete a course in military theory. In February 1890 he visited Paris in violation of the law of exile of 1886. He offered to do his military service as required by law. Instead he was arrested and confined in the Conciergerie. He was sentenced to two years in prison at Clairvaux, but was released after a few months and expelled back to Switzerland.
Prior to his imprisonment in France, Philippe had been unofficially engaged to his first-cousin Princess Marguerite of Orléans. The engagement was cancelled when Philippe's involvement with the Australian opera singer Nellie Melba was revealed. Although they had lived apart for some years, Melba was married to Charles Nesbitt Armstrong. Armstrong filed for divorce from Melba on the grounds of adultery, naming Philippe as co-respondent; the case was eventually dropped.
In September 1890 Philippe accompanied his father on a two month trip to the United States and Canada. They visited the battlefields of the Civil War in which his father had fought, as well as Philadelphia, Washington, D.C., Richmond, Virginia, New York, and Quebec.
In December 1890 Philippe tried unsuccessfully to serve in the Russian Army. In March 1893 he was elected a Fellow of the Royal Geographical Society.
In March 1894 Philippe went to Egypt and Palestine with his sister Hélène, Duchess of Aosta. Then he went lion shooting in Ethiopia. In May 1894 he was attached to the Royal Bucks Hussars, a yeomanry regiment.
In October 1895 Philippe was named as co-respondent in the divorce case of Woolston v Woolston.
On 5 November 1896 in Vienna, Austria, Philippe married Archduchess Maria Dorothea of Austria (14 June1867 - 6 April 1932), daughter of Archduke Joseph Karl of Austria, Palatine of Hungary, and granddaughter of Duchess Maria Dorothea of Württemberg. There were no children from this marriage. The couple were poorly matched; after several years they lived apart.
Philippe continued to reside in England until 1900, when he moved his primary residence to Belgium. He was an active yachtsman and explored parts of the western coast of Greenland in 1905. In 1907 he sailed in the Kara Sea north of Siberia, and in 1909 went even further north into the Arctic Ocean.
In 1914 Philippe and his wife Maria Dorothea were legally separated. She subsequently lived in Hungary.
At the outbreak of World War I Philippe tried again unsuccessfully to join the French Army. He was also refused permission to serve in the Belgian Army and instead returned to England. A plan to join the Italian Army was prevented by a serious accident in which he was knocked down by a bus.
He also published a collection of the papers of his father and of the Henri, comte de Chambord: