Barbara was born on 30 April 1539, in Vienna. She was daughter of Ferdinand I, Holy Roman Emperor, and his wife, Anna of Bohemia and Hungary. In 1547, Barbara and her sisters Magdalena, Margareta, Helena and Johanna moved to Innsbruck, where they received a deeply religious education.
Even though Barbara was considered plain, she received several proposals for her hand, due to her connection to the Austrian and Spanish courts. The chosen one was Alfonso II, Duke of Ferrara, and in 1565, their marriage was celebrated with much splendour. Barbara and Alfonso had a happy marriage, but they remained childless.
In 1570 and 1571, after an earthquake, the Duchess of Ferrara decided to use her own income to support young girls without parents. She was also responsible for the foundation of the Conservatore delle Orfane di Santa Barbara, which was very much appreciated by the population of Ferrara.
Barbara, deeply religious, was in constant touch with the Jesuits but, at the same time she had a very close relationship with her mother-in-law, the Protestant Renée of France.
Barbara's health started failing in 1566 and she had been sickly ever since. She died on 19 September 1572, aged 33, of tuberculosis.
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