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It is indeed necessary to develop a suitable bi-functional catalyst for total water splitting. Here, in this work, we demonstrate a microwave-assisted formulation of NiMoO4 nanorods within 30 minutes of the reaction time. As synthesized NiMoO4 nanorods grown on nickel foam were treated with NaBH4 to create internal oxygen vacancies [NiMoO4(Vo)] that favoured OER and HER with very merginal applied overpotential. The generation of oxygen vacancies in the lattice generally leads to the formation of an effective electronic structure for proceeding OER activity in a sustainable way. When vacancy-enriched NiMoO4(Vo) nanorods were applied for OER and HER under alkaline conditions, it demands only 220 and 255 mV overpotential at 50 mA cm−2 current density, respectively. Having observed their phenomenal response in both OER and HER, they were analysed for the real device as the two-electrode system …