A novel α-MoO₃/TiO₂ composite electrode material for high performance supercapacitor applications was synthesized using a facile electrodeposition technique. The surface morphology, microstructure, chemical composition and chemical states of the electrode material were analyzed using scanning electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. Cyclic voltammetry tests, galvanostatic charge–discharge measurements, and electrochemical impedance spectroscopy were employed to analyze electrochemical behavior. The results demonstrate that a very high capacitance (43.42 mF cm⁻²) can be achieved at a scan rate of 20 mV s⁻¹ in 1 M aqueous Na₂SO₄ solution and good capacitance behavior even after 3000 continuous charge–discharge cycles, indicating potential applications as an electrode material for supercapacitors.