The photochemical [2+2] cycloaddition of 3,5-bis-(2-(pyridin-4-yl)vinyl)pyridine (bpvp) in the flexible Cd-based metal-alkene frameworks produced different isomeric photoproducts depending on the auxiliary and guest molecules. The bulkiness of the guest molecules influenced the conformation of the ligand, and thus the outcome of the cycloaddition reaction.