AbstractOwing to the large storage capacity, the transparent luminescent glass with photo‐induced coloration properties has attracted considerable interest in recent years. However, lots of the photochromic (PC) mechanisms for glass are related to the ionic valence transformation, and the study associated with the defects‐induced photochromism of glass is limited. Herein, a kind of Sm3+ doped PC cadmium glass is fabricated, for which the PC mechanism is systematically investigated by various techniques, such as XPS spectra, thermoluminescence spectra, EPR spectra, etc. The results show that the mechanism of coloration for such glass should be due to the presence of oxygen vacancy‐related electron centers. Under 365 nm light irradiation, the color of the glass turns from colorless to brown, exhibiting a large color contrast, of 62%. Utilizing the re‐absorption process between absorption spectra and emission/excitation spectra, the emission intensity of Sm3+ is reversibly regulated, indicating their promising applications as an optical storage medium.