Educated at Derby School, St John's College, Oxford, the English college at Rheims and the Venerable English College at Rome, in October, 1583 James was ordained as a priest in Rome by Bishop Thomas Goldwell, the last survivor of the English bishops who had refused to accept the Protestant Reformation.
He was captured on board a ship at Littlehampton, Sussex, on 19 April 1586, with three other priests, Thomas Bramston, George Potter, and his fellow martyr, Ralph Crockett, and they were charged with being Catholic priests and coming into the realm of England, contrary to an Act of Parliament of 1584. All four were sent to London and put in prison there on 27 April 1586, where they remained for more than two years without trial.
After the failure of the Spanish Armada, an attempt to invade England which was defeated in July and August of 1588, the government of Queen Elizabeth I wanted revenge, and the priests in its custody became a target. Four of these, Ralph Crockett, Edward James, John Oven and Francis Edwardes, were sent for trial at Chichester on 30 September 1588. All four were condemned to death for being priests and entering England, but Oven then took the Oath of Supremacy, in accordance with the Act of Supremacy 1559, and was reprieved. On 1 October 1588, the other three were drawn on a hurdle to Broyle Heath, near Chichester, where Edwardes recanted and was also reprieved. Crockett and James continued to refuse to recant and to take the oath and were executed, after absolving each other.