The construction of perovskite-based wide bandgap semiconductors with uniform dispersion is one of the main strategies to improve the catalytic activity of semiconductor materials. Here, a heterojunction catalyst was obtained by nucleating TiO2 on CeCoO3 nanopowders and producing TiO2/CeCoO3 hetero nanostructures at 450 °C. Then by putting them on the PMO-IL as a porous substrate, TiO2/CeCoO3/PMO-IL nanohybrid was prepared. The properties of nanohybrid were characterized by FE-SEM, EDS, XRD, BET, XPS, HRTEM, SAED, FT-IR, DRS, and PL spectroscopy. The photocatalytic efficiency of TiO2/CeCoO3 and TiO2/CeCoO3/PMO-IL toward the selective fabrication of aldehydes was studied under the irradiation of visible light. The synthesized nanohybrid demonstrated excellent catalytic activity compared to TiO2/CeCoO3 and PMO-IL alone. Therefore, this nanohybrid could be used as a capable heterogeneous photocatalyst due to its high activity, selectivity, and recyclability.