Researchers are investigating innovative composite materials for renewable energy and energy storage systems. The major goals of this studies are i) to develop a low-cost and stable trimetallic oxide catalyst and ii) to change the electrical environment of the active sites through site-selective Mo substitution. The effect of Mo on NiCoMoO4 is elucidated using both in situ X-ray absorption spectroscopy and X-ray diffraction analysis. Also, density functional theory strategies show that NiCoMoO4 has extraordinary catalytic redox activity because of the high adsorption energy of the Mo atom on the active crystal plane. Further, it is demonstrated that hierarchical nanoflower structures of NiCoMoO4 on reduced graphene oxide can be employed as a powerful bifunctional electrocatalyst for oxygen reduction/evolution reactions in alkaline solutions, providing a small overpotential difference of 0.75V. Also, Zn-air batteries based on the developed bifunctional electrocatalyst exhibit outstanding cycling stability and a high-power density of 125.1mW cm-2 . This work encourages the use of Zn-air batteries in practical applications and provides an interesting concept for designing a bifunctional electrocatalyst.