He was born in Badoc, Ilocos Norte on October 23, 1857. He was educated at the Ateneo de Manila where he obtained his Bachelor of Arts degree in 1874 and was lured to study navigation and became a sailor. He sailed to various ports. He gave up sailing and studied painting at the Academy of Fine Arts and later went to Madrid in 1877 despite vehement protest of his parents.

At the National Exposition of Fine Arts in Madrid (1881), his painting, The Death of Cleopatra, was awarded second prize. However, the painting that won for Luna even greater international fame was the Spolarium. It was awarded first prize (gold medal) in the National Exposition of fine Arts held in Madrid in 1884 and the Battle of Lepanto won him another gold medal in the Barcelona Exposition of 1888. His last named painting is the El Pacto de Sangre (this portrays the blood compact between Legazpi and Sikatuna) obtained the first prize in Paris in 1885 and the St. Louis Exposition, USA in 1904. He married Paz Pardo de Tavera but he killed his wife and mother in law due to blind rage. He was acquitted in court.

Briefly he returned to the Philippines in 1894 but was arrested in 1896 due to alleged complicity in the Katipunan uprising but he was pardoned on the birthday anniversary of King Alfonso XIII. He left for Europe. When the Filipino American war broke out on February 4, 1899, he desired to come home and join the Filipino army but he died of a heart attack in Hongkong on December 7, 1899.