This work reports the self-assembly of three cadmium complexes 1–3 from one 2-substituted 8-hydroxyquinoline ligand (HL). The skeleton exhibits an unprecedented structural diversification and fabricates one mononuclear and two different tetranuclear Cd(II) building units in response to the counteranions NO₃⁻, OAc⁻ and I⁻, respectively. The self-assembly behavior of the cadmium salts and the HL in MeOH was subsequently investigated using UV-vis spectroscopy. In the solid state, the supramolecular structures of 1–3 feature unique helical chains or a 3D network via non-covalent interactions, such as π⋯π stacking, C–H⋯π, hydrogen bonding and halogen-related interactions. As a result, the three Cd(II) complexes exhibit disparate photophysical properties. This unique capability may provide a useful strategy to tune the optical properties of multinuclear materials, which could be exploited as important components for optoelectronic devices.