Her Royal Highness The Princess Charlotte Augusta Matilda was born at Buckingham Palace. She was styled Princess Royal from October 1766 and officially designated as such on 22 June 1789. Like her siblings, the Princess Royal was educated by tutors and spent most her childhood at Buckingham Palace, Kew Palace, and Windsor Castle.
On 18 May 1797, the Princess Royal was married at the Chapel Royal, St. James's Palace, London to His Highness the Hereditary Prince Friedrich of Württemberg, the eldest son and heir apparent of Duke Friedrich II Eugene of Württemberg and his wife, Princess Frederica of Brandenburg-Schwedt. The younger Friedrich succeeded his father as the reigning Duke of Württemberg on 22 December 1797. Duke Friedrich II had two sons and two daughters by his first marriage to the late Princess Augusta (3 December 1764-27 September 1788, the daughter of Duke Karl II of Brunswick-Wolfenbüttel and Princess Augusta of Great Britain and Ireland (the only sister of King George II) and the younger sister of Caroline of Brunswick, the estranged wife of the future King George IV (then the Prince of Wales). The marriage between Duke Friedrich and the Princess Royal produced one child: a stillborn daughter on 27 April 1798.
In 1800, the French army occupied Württemberg and the Duke and Duchess fled to Vienna. The following year, Duke Friedrich concluded a private treaty ceding Montbeliard to France and receiving Ellwanger in exchange two years later. He assumed the title Elector of Württemberg on 25 February 1803. In exchange for providing France with a large auxiliary force, Napoleon recognized the Elector as King of Württemberg on 26 December 1805. Electress Charlotte became Queen when her husband formally ascended the throne on 1 January and was crowned as such on the same day at Stuttgart, Germany. Württemberg seceded from the Holy Roman Empire and joined Napleon's short-lived Confederation of the Rhine. However, the new elevated king's alliance with France technically made him the enemy of his father-in-law, George III. Queen Charlotte, incensed by her son-in-law's assumption of the title and his role of one of Napoleon's most devoted vassals, refused to address her daughter as "Queen of Württemberg" in correspondence. In 1813, King Friedrich changed sides and went over the Allies, where his status as the brother-in-law of the Prince Regent (later George IV) helped his standing. After the fall of Napoleon, he attended the Congress of Vienna and was confirmed as King. He died in October 1816.
The Dowager Queen of Württemberg continued to live at the Ludwigsburg Palace, Stuttgart and received visits from her younger siblings, the Duke of Kent, the Duke of Sussex, the Duke of Cambridge, the Landgravine of Hesse-Homburg (nee Princess Elizabeth of Great Britain), and Princess Augusta of Great Britain. She was a godmother (by proxy) at the christening of her niece, Princess Victoria of Kent (the future Queen Victoria), in 1819. In 1827, she returned to Britain for the first time since her wedding in 1797 in order to have surgery for dropsy. She died at Ludwigsburg Palace the following year and is buried there in the royal vault.