Adelgundes married Prince Henry of Bourbon-Parma, Count of Bardi, fourth child and youngest son of Charles III, Duke of Parma and his wife Princess Louise Marie Thérèse of France, on 15 October 1876 in Salzburg, Austria–Hungary. Henry, who was 25 years old, had been previously married to Princess Maria Immacolata of Bourbon-Two Sicilies, who had died three months after their marriage at the age of 19 in 1874. Henry had taken part in the Carlist war and fought in the Battle of Lacar. War wounds turned him into an invalid.
Their union produced no issue, as her nine pregnancies all ended in miscarriages. The failed pregnancies, the last of which she suffered in 1890, were a source of great grief to the couple. They divided their time between the Castle of Seebenstein in Austria and the Vedndrami-Caligari palace in Venice. Adelgundes spent long years looking after her paralyzed husband. The Count of Bardi was described by relatives as a disagreeable man who tyrannized his sweet, petite wife. After almost 30 years of marriage, Adelgundes became a widow in 1905.