A metal-organic compound [Cd(quin)2(4-nvp)2] [1; Hquin = quinoline-2-carboxylic acid and 4-nvp = 4-(1-naphthylvinyl)pyridine] undergoes topochemical [2 + 2] cycloaddition by sunlight irradiation to generate a one-dimensional coordination polymer. This reaction is thermally reversible, and switching between two crystalline forms can be monitored by conductivity measurements.