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Little is known about Alarcón's life outside of his expedition in New Spain. He set sail on May 9, 1540 with orders from the Spanish court to await at a certain point on the coast the arrival of an expedition by land under the command of Francisco Vasquéz de Coronado.
He sailed into the Gulf of California, which had been explored the previous summer by Francisco de Ulloa. He made a careful survey of the coast, ascended the Colorado (then called the Rio del Tizon or Rio de Buena Guia) for 85 Spanish miles. The meeting with Coronado was not effected, however, although Alarcón reached the appointed place and left letters, which were afterwards found by Melchior Diaz, another explorer.
Alarcón was the first to determine with certainty that Baja California was a peninsula and not an island, as had been supposed. Upon his return to New Spain in 1541 he constructed a more accurate map of California depicting it correctly as a peninsula. Nevertheless, the notion of the Island of California peristed on many European maps well into the 18th century.