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In 1808, after a period of shaky alliance between the Spanish Antiguo Régimen and the Napoleonic French First Empire, the Mutiny of Aranjuez (17 March 1808) removed the king's minister Manuel de Godoy, Prince of the Peace, and led to the abdication of king Charles IV of Spain (19 March 1808).
She married in the Escorial, Madrid, 2 October 1797 Don Manuel de Godoy y Álvarez de Faria, 1st Principe de la Paz, 1st Duque de Alcúdia and 1st Duque de Sueca (Badajoz, 12 May 1767 – Paris, 4 October 1851), and had issue, an only daughter Carlota Luisa Manuela.
Napoleon took advantage of the weak king by suggesting the two nations conquer and divide Portugal, with France and Spain each taking a third of the spoils, and the final third going to the Spanish Prime Minister Manuel de Godoy, along with the title Prince of the Algarve.