In this study, we investigate the influence of calcination temperature on the structural, optical, and electrochemical properties of Mn3O4 nanoparticles synthesized through a chemical co-precipitation route. Field-Emission Scanning Electron Microscopy (FESEM) images depict the formation of highly agglomerated, spherical-shaped particles. At calcination temperatures of 700 °C and 900 °C, the observation reveals the emergence of flat pellets and rod-like structures. The X-ray Diffraction (XRD) patterns confirm the presence of the Mn3O4 phase in M0 and M1 samples. However, the sample calcined at 500 °C (M3) showed a mixed phase of Mn3O4 and Mn2O3. Upon further calcination at 700 and 900 °C, this mixed phase undergoes complete transformation into the Mn2O3 phase. The change in absorption onset and photoluminescence intensity of samples is found with an increase in calcination temperature due to the crystal growth and phase modification. Furthermore, the synthesized samples are employed as electrode materials for supercapacitor applications. The sample calcined at 300 °C (M1) in three-electrode system demonstrated the specific capacitance (Csp) of 273.3 F/g at 0.5 A/g in an alkaline medium. The asymmetric cell assembled by using M1 and Hibiscus cannabinus stem-derived carbon material (HBC-900) delivered higher Csp of 205.7 F/g at 0.5 A/g. In addition, asymmetric supercapacitor device exhibited a high energy and power density of 43.1 Wh/kg and 476.2 W/kg with 82.07 % of initial Csp retention over 10,000 cycles at 10 A/g, which makes the sample M1 as the potential electrode material for supercapacitor application.