Solid state [2 + 2] cycloaddition photochemical reactions have recently emerged as a benign green method to synthesize cyclobutane derivatives. Synthesis of cyclobutane isomers are often controlled by the manner in which unsymmetrical olefin pairs have been aligned either in a head-to-head (HH) or head-to-tail (HT) manner using bridging ligands, organic templating agents, metalorganic clipping agents, and metallophilic interactions. Here we synthesized three Zn(II) one-dimensional coordination polymers (1D CPs) in which the terminal ligands having olefin groups are aligned in both a HH and HT fashion to undergo a photo-cycloaddition reaction. Of these, two CPs provided HH photoproducts, while the third CP gave a mixture of HH and HT photoproducts. These results hope to provide additional knowledge to design the solids to obtain the desired cyclobutane regioselectively.