In 2008 on the death of his father, HRH Prince Carlo Maria, Duke of Calabria, succeeded his father as Duke of Castro, and Head of the Royal House of Bourbon Two Siclies. On his succession Prince Carlo who had previously served as Grand Prefect of the dynastic Orders of the Royal House of Bourbon Two Sicilies became Grand Master.

The Duke and Duchess of Castro play an active role in the day-to-day activities of the dynastic orders and their representation at home and abroad. In 1998, Prince Carlo married Miss Camilla Crociani in Monte Carlo, Monaco, who by marriage became and following her husbands succession became Her Royal Highness Princess Camilla of Bourbon Two Sicilies, Duchess of Castro.

Their Royal Highnesses currently have two children, HRH Princess Maria Carolina Chantal, Edoarda, Beatrice, Januaria of Bourbon Two Sicilies (born in Rome in 2003) and HRH Princess Maria Chiara Amalia Carola Louise Carmen of Bourbon Two Sicilies (born in Rome 2005).