The porous structure of three-dimensional NiO microspheres on titanium carbide (NiO/Ti3C2Tx) is prepared by calcination of Ni-MOF/Ti3C2Tx in the air. The crystalline structure and morphology of the obtained hybrid are characterized with various tools such as X-ray photoelectron spectroscopy and X-ray diffraction, scanning electron microscope, transmission electron microscope, and Brunauer-Emmett-Teller surface analyzer techniques. As-prepared NiO/Ti3C2Tx hybrid is used for two noteworthy applications in electrochemistry like supercapacitor and non-enzymatic hydrogen peroxide (H2O2) sensor. NiO/Ti3C2Tx electrode exhibited an enhanced specific capacity of 630.9C g−1 at a current density of 1 A g−1 in comparison to pure NiO (376.8C g−1). Furthermore, the H2O2 sensing performance of the NiO/Ti3C2Tx modified glassy carbon electrode is evaluated in 0.5 M of NaOH solution and the electrode showed a low detection limit of 0.34 μM with a wider range of linear response 10 μM to 4.5 mM. The higher specific surface area and porosity of NiO/Ti3C2Tx allow more electro-active site for electrochemical redox reactions in the direction of H2O2 sensing and supercapacitor. Moreover, Ti3C2Tx prevents from fouling in 3D porous network and leaching effect, and beneficial for easy access of electrolyte ions and efficient electron transport to the electrode surface resulted in improved electrochemical applications.