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While travelling in Spain, Alvear's brothers and mother died in an incident that took place on October 5, , when English frigates opened fire on the Spanish ship that was transporting them. This incident was a preamble to the Battle of Trafalgar and the consequent war between both countries. The English took Alvear and his father, together with other survivors, as prisoners to England, where Diego de Alvear would later marry an Irish woman. Notwithstanding the fate of his mother and brothers at the hands of the English, year-old Carlos was partially educated in the English culture, adopting, in his adult age, what some would later see as a position partial to English interests.
Like many other nineteenth century Argentines prominent in public life, he was a freemason. Alvear was one of the few professional military officers to participate of the Argentine War of Independence on the side of the revolutionaries, having served in the Spanish Army during the Napoleonic Wars. He became an active Freemason. Upon his arrival, Alvear was named Lieutenant Coronel of the young Argentine army.
Alvear was a leader of the constituent Assembly of the year and, goaded by political ambition, succeeded in establishing an Unitarian centralizing form of government, having his uncle Gervasio Antonio de Posadas named Supreme Director chief executive.
In early , Alvear was appointed commander in chief of the forces defending the capital. It was the biggest victory for the cause of independence since He was only 25 and the most successful general of the revolution.
He returned to Buenos Aires to claim his laurels but a revolt forced him back to the Banda Oriental. After a quick and decisive campaign, his forces defeated the caudillos that opposed the government. At the end of Alvear was named commander of the Army of the North , but he lacked of support from Posadas, and his unpopularity among the troops, and other disagreements—including a project for a constitutional monarchy that he sent to Europe to be negotiated by Manuel Belgrano , that was fiercely opposed by the League of Free Peoples —made him return to Buenos Aires.