Extended exposure to sunlight may give rise to chemical and physical damages of human hairs. In this work, we report a novel method for non-destructive quantification of hair photodamage via multispectral imaging (MSI) technology. We show that the multispectral reflectance value in near-infrared region has a strong correlation with hair photodamage. More specifically, the hair segments with longer growing time and the same hair root segment after continuous ultraviolet (UV) irradiation displaying more severe photodamage observed via scanning electron microscopy (SEM) micrographs showed significantly higher multispectral reflectance value. Besides, the multispectral reflectance value of hair segments with different growing time was precisely reproduced by exposing the same hair root segment to specific durations of UV irradiation, suggesting that MSI can be adequately applied to determine the sunlight exposure time of the hair. The loss of cystine content of photodamaged hairs was identified to be the main factor that physiologically contributed to the morphological changes of hair surface fibers and hence the variation of their multispectral reflectance spectra. Considering the environmental information recording nature of hairs, we believe that MSI for non-destructive evaluation of hair photodamage would prove valuable for assessing sunlight exposure time of a subject in the biomedical fields.