Precise arrangement of the aromatic donor-acceptor units is of paramount importance to dictate the performance of multi-component π-functional materials. Herein a novel strategy has been developed toward alternate donor-acceptor copolymers, by incorporating Pt(ii)Pt(ii) metal-metal interactions for the hetero-complexation process. The proximity of Pt atoms endows the resulting supramolecular copolymers with metal-metal-to-ligand charge-transfer transitions in the visible/NIR region. The signals have been further applied for low-energy visible-light photo-catalysis that is unattainable for the individual species. More interestingly, "on-demand" photo-catalytic efficiency can be achieved by manipulating the reversibility of the supramolecular copolymerization process. Hence, the current work demonstrates the efficiency of fabricating multi-component π-functional materials via the elaborate manipulation of non-covalent driving forces.