The purpose of this investigation was to study the ultraviolet A-induced effects on melanin pigmentation both in an in vitro model system and in vivo. Ultraviolet-Vis absorbance spectra of L-3,4-dihydroxyphenylalanine-melanin solutions at different concentrations were measured before and after ultraviolet A exposure (10-120 J per cm2). The difference spectra reveal that following ultraviolet A exposure the absorbance increases exponentially from 800 nm to 450 nm accompanied by a prominent decrease of absorbance in the ultraviolet A range. This change of spectral features depends on both ultraviolet A doses and melanin concentrations. The photo-bleaching effect observed in the ultraviolet A range also depends on oxygen. Human subjects were irradiated with ultraviolet A (40-80 J per cm2) on their back and diffuse reflectance spectra were collected at both irradiated and untreated sites. The absorption spectra of ultraviolet A-induced pigment were calculated as the difference of the two. The ultraviolet A-induced pigment in vivo has similar spectral characteristics and dose dependency as the in vitro system. Photo-oxidation of pheomelanin solutions presents distinctively different spectral and dose-response characteristics from eumelanin. After ultraviolet A irradiation pheomelanin absorbance decreases both in the visible and the ultraviolet A range. We conclude that irradiation with ultraviolet A induces significant photochemical alterations in the skin witnessed by increased photoprotection in the visible spectral range and reduced protection in the ultraviolet A range. We suggest that soluble melanin plays an important part in ultraviolet A-induced pigment in skin and two distinct absorption mechanisms of melanin may be involved in ultraviolet A photo-oxidation. We also propose that eumelanin and pheomelanin could be differentiated according to their spectral responses to ultraviolet A irradiation.