Interlinking discrete supertetrahedral chalcogenolate clusters with conjugated bipyridine linkers form a one-dimensional coordination polymer, [Cd6Ag4(SPh)(16) (DMF)(H2O)(bpe)](n) (1a), displaying a broader visible-light absorption and a narrower band gap than those of the discrete cluster. More importantly, the coordination polymer demonstrates enhanced activity and stability for the photocatalytic degradation of organic dye in water.