We report the first instance of observing the phototriggered isomerization of dmso ligands on a bis sulfoxide complex, [Ru(bpy)₂(dmso)₂], in the crystalline solid state. The solid-state UV-vis spectrum of the crystal demonstrates an increase in optical density around 550 nm after irradiation, which is consistent with the solution isomerization results. Digital images of the crystal before and after irradiation display a notable color change (pale orange to red) and cleavage occurs along planes, (01) and (100), during irradiation. Single crystal X-ray diffraction data also confirms that isomerization is occurring throughout the lattice and a structure that contains a mix of the S,S and O,O/S,O isomer was attained from a crystal irradiated ex situ. In situ irradiation XRD studies reveal that the percentage of the O-bonded isomer increases as a function of 405 nm exposure time.