<p>The perovskite like LaMnO₃ is synthesized by the citrate gel auto-combustion route and further utilized to attain its composite materials with prepared reduced graphene oxide (rGO) as LaMnO₃/rGO (25–75%). The calcination temperature to achieve the monophasic LaMnO₃ material is ascertained by Thermogravimetric-Differential Thermal Analysis (TG–DTA) of gel precursor. The as synthesized LaMnO₃, rGO and LaMnO₃/rGO (25–75%) composite materials are well characterized by the X-ray diffraction (XRD) and Fourier Transform Infra-Red (FTIR) spectroscopic techniques. The textural morphology of the materials is ascertained by Scanning Electron Microscopy (SEM). The electrochemical performance of the material is further investigated by Cyclic Voltammetry (CV), Galvanostatic Charging Discharging (GCD) and Electric Impedance Spectroscopy (EIS). The LaMnO₃/rGO75% is found to be a promising candidate for its use in supercapacitors owed to its unique anion-based intercalation capacitive behavior. The LaMnO₃/rGO75% has exhibited a high specific capacitance of around 641 F/g at a current density of 1 A/g and possesses ≈99% specific capacitance retention after 1000 charge–discharge cycles holding a great potential for utilization for energy storage devices.</p>