The photochemical [2+2] cycloaddition reaction of olefinic bonds within their frameworks of the solid coordination polymers currently remains one of the hottest topics in chemistry.1 However, it is currently difficult to rationally design a molecule that crystallizes in an arrangement suitable for the desired photoreaction.Works involved in creating controllable SCSC photodimerizations within coordination polymer networks has been rare until now.Herein we report our recent progress in this respect.