In this work, we synthesized α-MoO3 rods and studied their supercapacitive properties. The synthesized material was characterized using different experimental techniques. The optical band gap of the synthesized material was found to be 4.8 eV. Scanning electron microscopy (SEM) revealed that the synthesized rods have an average length of 2.6 µm and a width of 0.26 µm. Cyclic voltammetry (CV) measurements displayed two distinct redox peaks, indicating the pseudocapacitive nature of the material. The CV curves remained stable even at higher scan rates, indicating better stability of the electrode. Galvanostatic charge–discharge (GCD) analysis yielded a specific capacitance (SC) of 270 F/g at a current density of 1 A/g. It retains 85% of its initial SC after 2000 cycles. Electrochemical impedance spectroscopy (EIS) revealed a low charge transfer resistance, indicating good conductivity and efficient ion transport. An asymmetric supercapacitor device (MoO3//AC) was assembled using MoO3 as a positive electrode and activated carbon (AC) as a negative electrode to demonstrate its practical application. Device delivered energy density of 7.5 Wh/kg at a power density of 400 W/kg. The pseudocapacitive behavior, high specific capacitance, and good stability make α-MoO3 as a promising candidate for supercapacitor applications.