The photoexcited charge-transferred state of [AuCl(PPh(3))(2)] in a novel polymorphic crystal form was directly observed by X-ray photocrystallographic analysis. Its photoexcited state was completely different from the one generated in the known crystal of [AuCl(PPh(3))(2)]; the photoexcited bond-shrunk state was generated in the known crystal. This difference in the generated photoexcited state was clearly reflected by the difference in emission color. While the known crystal form showed green phosphorescence, the novel form showed blue phosphorescence under UV irradiation. The difference in the generated photoexcited state was due to the differences in steric hindrance in the crystal; bond shortening by photoexcitation was sterically allowed in the known form, while on the other hand, it was restricted in the novel form. Therefore, instead of the bond-shrunk state, the charge-transferred excited state became the lowest triplet state, and the emission color changed from green to blue (i.e., a blue shift of the emission wavelength was observed). These results mean that the photoexcited structure and the emission color of [AuCl(PPh(3))(2)] can be controlled by designing the molecular environment in the crystal.