In 1533, he signed a contract with his proprietor which allowed him to seek new chances as a conquistador and allowing him to come back after four years with profits. Juan arrived in Guatemala and participated in Pedro de Almagro's expedition. He arrived in Chile with Almagro, and joined Pedro de Valdivia's company.
Valiente contributed to establish Santiago de Chile in 1546 and was compensated with a ranch on the outskirts. Four years later, he received a commission and he made up a family with Juana de Valdivia, an Africa former slave, once belonging to a governor. In Chile, he made a certain fortune and could live freely. Nonetheless, Alonso Valiente had not forgotten his business deal. Valiente conceded him a new installment, and in 1541, sent a grandson of his to negotiate with his slave a reasonable price to liberate him from his property. However, Juan never forgot his slave condition and tried to pay; but due to a corrupt official, he was unable to do so. Alonso Valiente insisted on recovering his money, but it was too late, Juan Valiente had died and was laid to rest in Araucania.