[1] She was built in Havana, Cuba in 1794 as part of the Santa Ana class designed by Romero de Landa.

She left Havana on 26 February 1795 under the command of Brigadier Adrián de Valcárcel, and arrived in Cádiz on 17 May 1795 after escorting a valuable convoy.

While making their way back they encountered and were defeated by a British squadron on 14 February 1797 at the Battle of Cape St Vincent, The Príncipe de Asturias had 10 killed and 19 wounded, and helped save the Spanish flagship, the Santísima Trinidad, while it was under attack by British Commodore Horatio Nelson.

At the Battle of Trafalgar, she was part of the Franco-Spanish fleet and the flagship of Spanish Teniente General Federico Gravina, with Antonio de Escaño as his deputy and Brigadier Rafael Hore as the ship's captain.

She was the flagship of Juan Ruiz de Apodaca during the capture of the Rosily Squadron of the French ships of the line Neptune, Algesiras, Argonaute, Héros, Plutón and the frigate Cornélie.