She spent her childhood in the Blue Palace in Warsaw and Powązki. Since 1784 to 1793 Maria was married to Duke Louis of Württemberg, who became the Hetman of the Lithuanian Army in the 1792 war against Russia. Maria divorced him when his betrayal of the Polish-Lithuanian Commonwealth became known.
Maria"s only son, Duke Adam of Württemberg, remained with his father and was raised in an atmosphere prejudiced against his mother and Poland.
Following her divorce, Maria lived mostly in Warsaw, and since 1798 to 1804 spent winters in Vienna and summers at Puławy. Between 1808-1816 she hosted her literary salon in Warsaw (Blue Saturdays).
Her guests included Julian Ursyn Niemcewicz. She attended meetings of the Xs Society (Towarzystwo Iksów).
In 1816 she published Malvina, or the Heart"s Intuition, considered Poland"s first psychological novel.
Charmed with the picturesque village of Pilica she bought it and remodelled its landscape garden. The park in Pilica was considered among the most beautiful in Europe, and rivalled other parks in Poland: Powązki (established by Maria"s mother) and Helena Radziwiłł"s Arkadia. Maria hired Franciszek Lessel as her land agent.
Maria Wirtemberska was an active philanthropist.
She provided education and published calendars for the peasants. Following the November Uprising Maria moved to Sieniawa, then in Galicia.