James was born in Stoke Newington, London, to William and Elizabeth Alice Spensley.
He travelled extensively in his youth, and in combination with his medical practice, worked as a reporter for the Daily Mail. James also became a member of the Society of Antiquaries of Newcastle upon Tyne (SANT) in March 1893.
James is considered to be one of the 'Fathers of Italian football', establishing and becoming the first manager of Genoa CFC in 1897. In 1898, he led Genoa to the first Italian football championship title as player-manager, and the team went on to win a further five titles under his tenure.
As an acquaintance of Robert Baden-Powell, James helped establish the Italian branch of the Scouting movement in 1910.
James served as a doctor in the Army from the outbreak of the War, attaining the rank of temporary Lieutenant on 4th May 1915, seeing action in the Dardanelles Campaign.
He was injured on the battle field while tending to the wounds of an enemy out of compassion, and is believed to have been taken prisoner. James died of his wounds in German captivity on the 10th November 1915, aged 48 years old.