According to Argentine writer Vicente Gregorio Quesada [es], Montero took art lessons from Roberto Tiller, an American prisoner at Piura Prison for counterfeiting. He moved to Lima in 1844, working at the Casa Dorca y Barreda for one year, studying under Ignacio Merino in 1845.[1]
It is said that one of his paintings, a miniature portrait of then president Ramón Castilla, eventually reached him, with Castilla summoning Montero to the Government Palace and asking him why he had been painted so fair when his colour was "diverse" (Castilla was a mestizo of Aymara descent). While speaking to the President, the young painter confided his wish to study art, but not having the resources to do so. Castilla granted him a scholarship of 500 annualpesos fuertes to study in Europe, the first such grant in Peruvian history. Montero left for Europe in late 1848.[1]
In 1852, he was named director of the Academia de Dibujo, but was granted another scholarship to continue studying in Florence by José Rufino Echenique less than a year later. He was made a facultative member of the Lyceum in Havana, where he met Juana López, whom he married the same day he won the lottery. He returned to Peru in 1858 and left for Europe again two years later.[1]