Solar energy-harvesting materials have significantly contributed to the development of energy-saving applications for several decades. We have mainly used a new concept composed of the electrophoretic deposition technique and photonic crystal structural engineering to understand the tunable light-absorption and electronic conduction properties. A hexamolybdenum cluster compound (denoted as the Mo6 cluster) was successfully functionalized on a tin pyrophosphate semiconductor integrated within an inverse opal photonic crystal. The size of the periodical pores, surface modification, and chemical composition of the infiltration material of the inverse opal film have been investigated to control the photonic bandgap in the visible range and the efficiency of the deposited Mo6 cluster. The photoactive Mo6 clusters act as a visible light harvester and generate an efficient photo-induced current upon light absorption that is enhanced by a slow photon effect occurring at the photonic stopband edges. The electron and proton are transferred in the inorganic-organic network via hydrogen bonds by a hopping mechanism to generate a rapid photoconductivity response during light irradiation. Specific attention focused on the role of humidity and temperature regarding the reproducibility of the experiments and the photosensitivity of the nanocomposite. The suitable tunable photo-induced conduction property in organic-inorganic materials opens a new opportunity for the applicability of cluster-based compounds in visible optoelectronic devices.