Subjective color analysis is affected by factors such as lighting sources and observers. To avoid this subjectivity, the pigments of ancient murals are identified using visible spectroscopy, and the characteristics and historical evolution of the ancient murals'' color are then analyzed objectively using the chromatic theory. We built a nondestructive acquisition system and used it to capture the visible spectra of the typical Mogao Grottoes murals painted in different dynasties. Many typical pigment samples were prepared by simulating the ancient process. The visible spectra and particle sizes were measured to construct a standard reference database from the obtained results. After analyzing the relationships among the visible spectra, material composition, particle size, and color attributes, a pigment identification method was proposed to identify the pigment used on the murals. The color attributes and historical evolution of the Mogao Grottoes murals were analyzed by comparing the identified pigments with those in the reference database.