Born Count Ludwig Adolf Peter of Sayn-Wittgenstein-Ludwigsburg, he was descended from a family of independent counts whose seat was in Berleburg (present day North Rhine-Westphalia, Germany). His parents were Count Christian Louis Casimir of Sayn-Wittgenstein-Ludwigsburg and his first wife Countess Amalie Ludowika Finck von Finckenstein.

In 1805, he fought at Austerlitz, in 1806 against the Turks and in 1807 against Napoleon at Friedland and against the Swedes in Finland.

In the war of 1812 he commanded the right wing army of the Russians which he commanded in the First and Second battle of Polotsk. It was a battle that eventually decided faith of Saint-Petersburg, and the whole Napoleonic Russian Campaign of 1812. In the campaign of 1813 in January he took over the command of the Russian army after Kutuzov's death and commanded the Russian army at Lützen and Bautzen. But after the defeats of the Spring campaign he laid down this command and led an army corps during the Dresden and Leipzig campaigns, and at Bar-sur-Aube in the 1814 campaign he was severely wounded. In 1823 he was promoted Field Marshal, and in 1828 he was appointed to command the Russian army in the war against Turkey. But ill health soon obliged him to retire. In 1834 the king of Prussia gave him the title of Fürst (Prince) zu Sayn-Wittgenstein.

On 27 June 1798 he married Countess Antonia Cäcilie Snarska and had in this marriage 11 children.

He died on 11 June 1843 in Lemberg (Lviv), where he looked after estates of his son Lev Petrovich.