After the victory of Caseros, Charlone enlisted in the army of Buenos Aires, engaging in a war against the other Argentine provinces united under the leadership of the caudillo Justo José de Urquiza.

Placed at the head of a company of Grenadiers of the 2nd Line Infantry Battalion, he took part in the defense of the Argentine capital besieged by the forces of General Hilario Lagos.

This department, composed mainly of Italians, had been sent by Bartolomé Mitre in the southwest of the Bonaerense territory to protect the city of Bahía Blanca which was under construction but suffered from attacks by the natives.

In the clash, Chiarlone, who with a risky maneuver was the first to throw himself into the midst of the enemy defenses, was wounded in the head by a saber blow.

[4] Despite the wound and high casualties, he was rescued by his soldiers and evacuated with the rest of the Argentine troops at the end of the battle.

In 1866, with the beginning of the Humaitá campaign, Chiarlone and the Italian Military Legion faced the Paraguayans at the Battle of Tuyutí where the colonel commanded the 2nd Brigade of the Argentine 1st Army Corps at Yataytí-Corá and at Boquerón.