ABSTRACT Morphology of Mn3O4 is tuned to the nanoparticles / nanorods / nanofiber if ratio of metal precursor to polymer is varied from 0.33:1 to 2:1 in electrospinning solution. The best optimized nanofiber of Mn3O4 in terms of surface area, pore size and its distribution, and aspect ratio are obtained when equal amount of metal precursor and polymer (MN1:1) in electrospinning solution is taken, and sintered precisely at 1°Cmin−1. The structural, morphological and thermal characterizations are carried out by XRD, FESEM, TEM, SAED, BET surface area and TG analysis. Further, these morphologies of Mn3O4 are subjected to the electrochemical characterization for evaluating the supercapacitive performance. The value of specific capacitance of MN1:1 is found to be 210 (±5)Fg−1 and 155 (±5)Fg−1 at 0.3Ag−1 in 1M KCl and 1M Na2SO4, respectively. Improved supercapacitive performance of MN1:1 in both electrolytes is attributed to the unique nanofibric morphology where small nanoparticles are interconnected with good amount of open pores and forms a porous, one dimensional and high aspect ratio nanofibers. Electrochemical impedance spectroscopy (EIS) shows very low charge transfer resistance in MN1:1 favorable for fast and facile transportation of electrolyte ions to electrode and vice versa.