On July 11, 1533 Pope Clement VII excommunicated England's King Henry VIII. From the article:
"11 July 1533 - The Pope puts his foot down with Henry VIII - The Anne Boleyn Files
By 11th July 1533, Pope Clement VII had really had enough of King Henry VIII’s behaviour.
The king who had been awarded the title “Fidei Defensor” (Defender of the Faith) by Pope Leo X in 1521, for defending the Catholic Church against the works of Martin Luther, had not only abandoned his first wife without an annulment from the Pope and remarried, Convocation had granted him the title of Supreme Head of the Church in England. Pope Clement was not impressed.
On 11th July 1533, the Pope declared that Henry VIII’s marriage to Anne Boleyn was null and void, as was the annulment declared by Archbishop Thomas Cranmer in May 1533, and he restored Catherine of Aragon to her “royal state”. He ordered the wayward king to abandon the newly crowned and pregnant Anne Boleyn and return to Catherine of Aragon. If the king refused then the Pope would issue the bull of excommunication that he had drawn up. He’d give Henry until September to sort himself out, but if he didn’t heed the Pope’s warning then he’d be excommunicated, the most severe punishment that the Church could inflict.
Of course, Henry took absolutely no notice of the Pope, but he escaped excommunication until 17th December 1538 when Pope Paul III excommunicated him following his break with Rome, his persecution of those who did not accept his supremacy, the dissolution of the monasteries and Henry’s desecration of religious shrines including that of Thomas Becket."