The Spanish royal family were in the city to celebrate the marriage of her maternal uncle Ferdinand VII of Spain to Princess Maria Antonia of Naples on 6 October 1802.

Her mother, Maria Luisa, under difficulties gave birth to Maria Luisa Carlota (named after her deceased aunt, who had died four days before her mother's birth).

Her maternal grandparents and her uncle Ferdinand VII wanted to marry Maria Luisa Carlota, then fourteen years old, to the Infante Francisco de Paula, Maria Luisa's youngest brother; the marriage never materialised.

Maria Luisa Carlota married Maximilian, Hereditary Prince of Saxony, the widower of her aunt Carolina of Parma, in Lucca on 15 October 1825 (by proxy) and again in Dresden on 7 November 1825.

On 19 February 1855 she married again, Count Giovanni Vimercati, by whom she had no issue and who outlived her, dying in 1861.