Presented here is a photoactive cluster-organic frameworks with 1D Cu-I chain, namely (Cu2I)(pytz) (1) (Hpytz = 5-(4′-pyridyl)tetrazole). Compound 1 features a unique 1D Cu-I chain constructed from a Cu3I2 cluster. These chains are interconnected by the tetrazole moiety of pytz, forming a 2D layer. Furthermore, the pyridine moiety of pytz acts as pillars, creating a pillar-layered framework. Moreover, compound 1 displays strong photoluminescence, excellent visible light adsorption, and remarkable photocatalytic activity for the degradation of methylene blue under visible light conditions. These properties highlight the potential applications of these frameworks in areas such as optoelectronics and environmental remediation.