Her third marriage to Mr Díez - a civil servant 24 years her junior - in October 2011 was a source of fascination in the country, which has long been amused by her free spirited ways and outlandish dress sense.
The duchess was a distant relative of Queen Elizabeth, but - it is claimed - was more "noble". She holds the world record for the most aristocratic titles, being a duchess seven times over, a countess 19 times and a marquesa 23 times. Indeed, her full name is Maria del Rosario Cayetana Alfonsa Victoria Eugenia Francisca Fitz-James Stuart y de Silva.
As head of the 530-year-old House of Alba, she is entitled to ride her horse into Seville Cathedral, and according to protocol does not have to kneel before the Pope. Some genealogists even claim that the Queen must bow to her, owing to the fact that the duchess is descended from James II through his illegitimate son James Fitz-James, while the Queen is from the "upstart" Saxe-Coburg-Gotha line.
She had lost her first husband, Luis Martinez de Irujo y Artazcoz, in 1972. Her wedding to him in 1947 was considered the last great feudal wedding in Spain, with the cream of Spanish nobility gathering to witness the beautiful young heiress tie the knot with a dashing naval officer.
Following his death she married again, to Jesus Aguirre y Ortiz de Zarate - an intellectual and former Jesuit priest - but he died in 2001.
Her marriage to Mr Díez, in Seville Cathedral, was initially a source of concern for her children.
But prior to the wedding she divided up her vast wealth - thought to between £524m and £3bn - between them. Mr Díez also signed away any rights to the fortune.
She leaves behind an inheritance including vast properties in Madrid, Marbella, Ibiza and Seville - her main residence. Among the treasures is a collection of historical documents that include Columbus' first map of the Americas, and the last will and testament of Fernando the Catholic, as well as a library valued at €20.5 million that includes a first edition of Don Quixote from 1605, and a family Bible from 1429.
She also had one of the world's best private art collections, with works by Rembrandt, Reubens, Velazquez and Titian.
The duchess will be moved to the Salon Colon in Seville - the largest public space available for her funeral rites.