In the present study, nanoparticles filled with honeycomb-like MnCo2S4 (MCS) nanostructures are prepared successfully on the surface of nickel foam using a simple and cost-effective chemical bath deposition method and can be used as a promising electroactive material for high performance supercapacitor applications. The electrochemical behavior of the as-prepared electroactive materials was studied by the cyclic voltammetry, galvanostatic charge/discharge, electron impedance spectroscopy. The crystalline phase, structure, morphology and composition of the as-prepared electroactive materials were analyzed by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. The performance of the as-prepared electroactive materials was carried out in a 3 M KOH electrolyte in the three-electrode system. The unique nanoparticle structures enable and provides the more efficient pathways for the rapid mobility of electrons and ions. As a result, the as-prepared binder-free MCS electrode exhibits a higher specific capacity of 129.7 mA h g−1 at 1 A g−1, superior rate capability of 88.51% after 4000 cycles and excellent cycling stability of 87.81% respectively, which are much higher than that of MCO electrode. These results reveal that the as synthesized MCS electrode found to be the most promising candidate for high-performance supercapacitor applications.