Reported here are two X-ray photochromic metal chalcogenide frameworks, which consist of tetrahedral clusters that are linked by transition-metal amine chelates. They have similar structures, but with different organic amine species, and they exhibit different coloration behavior. The photoinduced electron transfer from the metal chalcogenide clusters to the zinc amine chelates is a key point in accounting for their photochromism. Interestingly, a high-contrast (up to 12.4 times) enhancement of the optoelectronic response is obtained for the title compounds after they are treated by X-ray irradiation.