His father, the explorer Dionisio Alcalá Galiano, was killed at the Battle of Trafalgar and his uncle, Don Juan María de Villavicencio [es], was Captain general of the Armada and a Regent of the Kingdom during the interregnum in the reign of Ferdinand VII.

Until then, he had been a great admirer of Montesquieu, but soon absorbed English ways of thinking, befriended Jeremy Bentham, became attracted to the moderate liberalism of Edmund Burke and rejected abstract principles in favor of utilitarianism, then adopted the doctrinaire liberalism of Alexis de Tocqueville and Benjamin Constant.

He returned to Spain in 1833, after Isabella II became Queen, and joined the Liberal cabinet of Juan Álvarez Mendizábal.

[2] He wrote a detailed autobiography, published posthumously in two versions: Recuerdos de un anciano (1878) and Memorias (1886).

His most notable work in that genre being Lecciones de literatura española, francesa, inglesa e italiana del siglo XVIII.