On 8 January 1859 in Munich at the Allerheiligen-Hofkirche Maria Sophie was married by proxy and then again married in-person on 3 February 1859 in Bari to the Duke of Calabria, the eldest son of Ferdinand II of the Two Sicilies, King of Naples. Within the year, with the death of the king, her husband ascended to the throne as Francis II of the Two Sicilies, and Maria Sophie became queen of a realm that was shortly to be overwhelmed by the forces of Giuseppe Garibaldi and the Piedmontese army.