Metal-organic framework (MOF)-based catalysts are gaining attention due to their tunable properties. In this study, we synthesized MOF based Ni and Co doped iron selenide (NiCoFeSe) hexagonal nanorods electrocatalyst. This NiCoFeSe catalyst exhibited outstanding performance in the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and urea oxidation reaction (UOR) with impressively low overpotentials of 220, 275 mV for HER, 230, 330 mV for OER, and 210, 300 mV for UOR at current densities of 50 and 100 mAcm, respectively. Additionally, we fabricate a wireless flexible and rigid photovoltaic-electrochemical device utilizing NiCoFeSe as both the anode and cathode, achieving an impressive solar-to-hydrogen efficiency of 11.1%. Furthermore, we developed an anion exchange membrane water electrolyzer with NiCoFeSe as anode and cathode, achieving a current density of 1.07 Acm at 1.85 V, along with a cell efficiency of 69.67% and an energy consumption of 47.85 kWh to produce 1 kg of hydrogen.