Born on 16 February 1786 in St. Petersburg to Paul I of Russia and his wife Sophie Dorothea of Württemberg. Maria Pavlovna was raised at her father's lavish palaces at Pavlovsk and at the nearby Gatchina.

She was the sister of:

As a child, she was not considered pretty: her features were disfigured as a result of a pioneering application of the Smallpox vaccine. Her grandmother, Catherine II of Russia, admired her precocious talent as a pianist but declared that she would have been better to have been born a boy. Her music instructor was Giuseppe Sarti (1729-1802), an Italian composer and Kapellmeister at the Russian court. From 1798, she was taught music by Ludwig-Wilhelm Tepper de Ferguson (1768-1838). In 1796 her grandmother died making her father the new Emperor of Russia as Paul I.

On 3 August 1804, she married Charles Frederick, Hereditary Grand Duke of Saxe-Weimar-Eisenach (later Grand Duke) (2 February 1783 – 8 July 1853). The couple stayed in St. Petersburg for nine months, before departing for Weimar. There Maria was greeted with a bout of festivities, as described by Christoph Martin Wieland: "The most festive part of all the magnificence of balls, fireworks, promenades, comedies, illuminations was the widespread and genuine joy at the arrival of our new princess".

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