Nicknamed Lina since her birth, the Princess spent the first years of her life under the supervision of her mother in the Austrian Imperial court at Vienna and was officially introduced there in society.

The choice finally fell on Prince Henry, Duke of Aumale, fifth and second-youngest son of King Louis-Philippe I of France and his wife Maria Amalia of the Two Sicilies, who became impressed with her during a stay at her father's palace in Naples.

[1] The marriage negotiations began in late August 1844, and on 17 September of the same year at the Revue de Paris, their engagement was officially announced.

The civil wedding was performed in the royal palace of King Ferdinand II of the Two Sicilies, and on the same day, the religious ceremony was celebrated with great pomp.

During the first months of 1845, which for Maria Carolina were filled by ceremonial duties at official occasions such as balls, theatrical performances or meetings with nobles, she and her husband had finally the opportunity to know each other better.

During that summer Queen Victoria and her husband were passing by France from their trip to Germany stayed for a night with the French royal family, according to her diary she describe of meeting Marie Carolina of the first time "who is a good bit smaller than me, very, very, fair & not at all pretty, but very pleasing; she has light blue eyes, a large nose & not a pretty mouth."

Maria Carolina soon become a close friend of Queen Victoria,[9] who gave her and her family the Orleans House in Twickenham, London, as their residence.

After a long journey in August 1864 across Europe (including Belgium, Germany, Austria, Hungary, Spain, Switzerland and the Orient), Maria Carolina preferably spent her time in the Wood Norton Hall estate at Worcestershire.

The unexpected death of her eldest son Louis Philippe, Prince of Condé, in 1866 plunged Maria Carolina into a deep depression from which she never fully recovered.