Grand Duchess Elena Pavlovna Romanova was born in Saint Petersburg in the Russian Empire as the fourth child and second daughter of Tsesarevich Paul Petrovich of Russia (1754–1801) and his second wife, Tsesarevna Maria Feodorovna, born Duchess Sophie Dorothea of Württemberg (1759–1828).
The formal betrothal was celebrated on 5 May 1799, and on 23 October 1799, they were married at the Great Gatchina Palace near Saint Petersbourg.
On 15 September 1800 she gave birth to her firstborn son, Paul Frederick, who would go on to inherit the throne of the grand duchy.
On 31 March 1803 she gave birth to a daughter, Marie Louise, named after her grandmothers, who would later become the duchess of Saxe-Altenburg.
Hereditary Princess Elena Pavlovna had two children with her husband, Hereditary Prince Frederick Louis (1778–1819), both of whom survived to adulthood: Elena Pavlovna's letters to her maternal grandfather, Frederick II Eugene, Duke of Württemberg, written between 1795 and 1797, are preserved in the State Archive of Stuttgart in Stuttgart, Germany.