She had four children with her husband, two of whom would survive infancy: the future Cosimo III, Tuscany's longest-reigning monarch, and Francesco Maria, a prince of the Church.

As an infant it was expected that she would inherit her grandfather's Duchy of Urbino, but Pope Urban VIII convinced Francesco Maria to resign it to the Papacy.

The marriage was arranged by the Grand Duke's grandmother, Christina of Lorraine, who had been acting as joint regent with her daughter-in-law Maria Maddalena of Austria since 1621.

Brought up in the convent of Crocetta, Vittoria's education was a deeply religious one administered by the Dowager Grand Duchesses who had aligned Tuscany with the Papal States.

[4] Shortly after the birth of Cosimo, the couple became estranged: Vittoria caught her husband and a page, Count Bruto della Molera, in bed together.

A son, Prince Ferdinando, and a daughter, Princess Anna Maria Luisa, were born within four years, and weeks after the accession of Cosimo III, Marguerite Louise was pregnant again.

[8] As a result, Vittoria was formally admitted into the Grand Duke's Consulta, or "Privy Council", leaving an embittered Marguerite Louise to her own devices.

[9] The two Grand Duchesses frequently quarrelled over precedence and the Consulta, but Cosimo III always took his mother's side, which only fuelled the ever-growing rages of Orléans.

By early 1671, fighting between Marguerite Louise and Vittoria became so heated that a contemporary remarked that "the Pitti Palace has become the devil's own abode, and from morn till midnight only the noise of wrangling and abuse could be heard".

Eventually, the Grand Ducal couple decided to separate on the condition that Orléans stay at the Abbey Saint Pierre de Montmartre in Paris.