The　ternary　combination　of　metal　cations,　CuI　and　viologen　based　carboxylate　leads　to　two　donor-acceptor　hybrid　heterostructures　with　novel　cuprous　iodide　clusters　and　narrow　energy　gaps.　Thanks　to　the　facilitated　electron　transfers　between　both　donor　and　acceptor　components,　these　unique　hybrids　exhibit　enhanced　photocatalytic　degradation　activities　towards　organic　dyes　under　visible　light　irradiation　in　comparison　with　those　of　bulk　CuI　and　viologen　semiconductors.　©　The　Royal　Society　of　Chemistry.