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She was the daughter of Antonio Giovanni Dolfin and Donata Salamon and a member of the Venetian aristocracy. She married Marcantonio Tiepolo in 1755. The marriage was arranged by her mother to solve the financial difficulties after the death of her father in 1753. In 1756, she entered in to a relationship with politician Andrea Tron, and filed for a divorce, which came through in 1772, upon which she married Tron. She was a "procuratoressa" by the position of her Andre Tron as procurector of St Marc, and as a public person subjected to certain libelous stories.
In 1757, she debuted as a writer under pseudonym. Her most famous work was a collection of sonnets inspired by her father, which was published in 1767-68. She was a center of a circle of intellectuals and held a prestigious literary salon. Among her guests was Gaspare Gozzi. Dolfin was described as beautiful and kind, admired for her brilliant conversation, her graceful poetry and prose. She was also an assistant of Gasparo Gozzi. In 1772, Dolfin was called before the Venetian Inquisition in because of her library of books of the enlightenment.
Dolfin was known for her love life and had from 1774 a known affair with duke Gian Galeazzo Serbelloni, who was then years her junior: their correspondence of love letters is preserved. There was a known occasion when Caterina Dolfin presented Princess Gonzaga, who had been the subject of many scandals, at the Venetian court: at first, the ladies of the Venetian aristocracy refused to accept her. Caterina Dolfin however, accepted to present her to them, and did so with the words: "Ladies, this is princess Gonzaga, she belongs to an illustrious family: as for the rest, I will not answer either for you nor for myself!"
In 1778, her spouse was elected senator. However he was not elected to doge in 1779 despite being one of two main candidates. This is partially attributed to the scandals surrounding her: at that time, she was known for her involvement in the Gratarol affair regarding secretary of state Antonio Gratarolo. In 1772, Gratarolo had defeated her own candidate for the post of ambassador to Savoy. Upon his return to Venice in 1775, he had an affair with actor Teodora Ricci, which made him a rival of Dolfin's friend, who wrote a libelous play about Gratarolo: this caricature was answer with another, which caricatured Dolfin and her circle and blackened her name and reputation publicly. In 1779, this damaged her spouse in the doge-election. The other candidate turned out to have a spouse regarded even more unsuitable as dogaressa, Margherita Delmaz, but is reported to have bribed her acceptance.
Caterina Dolfin was widowed in 1785. She was left a fortune as a widow, but became entangled in a dispute with her former in-laws. From 1788, she spent more time in her house in Padua. The last years, she worked on a project for the reform of female education, which dies not appear to have been finished before her death.
- Staley, Edgcumbe: The dogaressas of Venice : The wifes of the doges. London : T. W. Laurie
- Louisa Lauw: The Dogaressa
- La Serenissima: the last flowering of the Venetian Republic. Alfonso Lowe - 1974
- Dizionario Biografico degli Italiani - Volume 40 (1991)