Born on 16 February 1786 in St. Petersburg to Paul I of Russia and his wife Sophie Dorothea of Württemberg (Maria Feodorovna), she was named after her mother and their third daughter and fifth child. Maria Pavlovna was raised at her father's 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".

...
Wikipedia