Designing low cost, highly active and efficient non-noble metal bifunctional electrocatalysts with remarkable operational reliability for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is indispensable for large-scale water electrolysis and the development of clean energy conversion technologies. Herein, we decorated a two-dimensional (2D) selenium-blended zirconium dioxide (Se-ZrO2) on the surface of a nitrogen-doped carbon heterostructure (Se-ZrO2@NC), which was derived from Zr-metal-organic frameworks (Zr-MOFs), and loaded it on a stainless-steel mesh electrode. Accordingly, phenomenal electrocatalytic performance was observed for the Se-ZrO2@NC-loaded electrode with a minimum overpotential of 48 mV for the HER and 251 mV for the OER at 10 mA cm-2 current density in acidic and alkaline mediums, respectively. Moreover, a complete cell set up was constructed, where the OER and HER were studied at the anode and cathode, respectively, with a cell potential of 1.58 V to reach a current density of 10 mA cm-2 together with an exciting long-term stability of over 48 h. The developed Se-blended 2D transition metal dioxides on the 2D nitrogen-doped carbon heterostructure extended to a variety of catalytically active materials that would provide highly active and stable electrocatalysts for alkaline water splitting studies.