Recently, metal oxide-based nano-photocatalysts have gained a great deal of attention in waste water remediation due to their outstanding properties. In this report, a novel Mo-doped CuO nanomaterial was successfully prepared and utilized for the degradation of methylene blue water pollutant. The molybdenum content was varied from 1–5 wt.% to obtain the desired modified CuO based nanomaterials. The crystalline structures of as prepared materials were investigated using the XRD technique, which explored the successful fabrication of monoclinic-structure-based CuO nanomaterials. For morphological studies, SEM and HRTEM were used, which proved the successful preparation of nanoparticles-based material. SAED was used to check the crystallinity of the sample. EDX and XPS analyses were performed to evaluate the elemental composition of Mo-doped CuO nanomaterials. The optical characteristics were explored via UV-vis and PL techniques. These studies showed that the energy bandgap of CuO decreased from 1.55 eV to 1.25 eV due to Mo doping. The photocatalytic efficiency of Mo-doped CuO nanomaterials was evaluated by degrading methylene blue (MB) under visible light-irradiation. Among different Mo-doped CuO based nanomaterials, the 4 wt.% Mo-doped CuO sample showed the highest degradation activity against MB dye. These results verified that the optimized material can be used for photocatalytic applications, especially for the purification of waste water.