A comprehensive study on electroless Ni–P–Mo–TiO2 coating characteristics is conducted. From previous literature survey the inclusion of Mo within the Ni–P alloy for enhancing microstructural, friction, and wear performance is found to be already established. In this study, the composite is synthesized by incorporating TiO2 in the Ni–P–Mo alloy, and the microstructural, mechanical, and tribological properties are investigated. The coating has been deposited by the electroless method. The as-plated and annealed samples were characterized with EDS, SEM, and XRD to investigate the composition, morphology, and phase structure. The impact of annealing at 400 °C on the microstructural behavior was studied. Nano indentation was conducted to determine the mechanical characteristics such as their hardness and Young’s modulus to both as-deposited and annealed Ni–P–Mo–TiO2 coatings. The hardness of the heat-treated coating was 7.19 ± 3.52 GPa, which is much higher compared to as-deposited coating (1.32 ± 0.41 GPa). Same trend can be observed for elastic modulus as well. Heat treatment increased the reduced elastic modulus to 181.05 ± 38.1 GPa from 90.35 ± 14.7 GPa in as-deposited condition. The wear depth also reduced significantly after the heat treatment. The outcomes showed that, due to the incorporation of TiO2 and the annealing, the Ni–P–Mo–TiO2 matrix transformed into a superior coating with improved tribological behavior, suggesting potential applications in adverse environments.