Synthesis of rational nanostructure design of hybrid materials including uniformly growing, stable and highly porous structures have received a great deal of attention for many energy storage applications. In this study, the positive electrode of the uniform distribution of NiCo2O4 nanorods anchored on carbon nanofibers has been successfully prepared by in-situ growth under the hydrothermal process. Whereas, the activated multichannel carbon nanofibers (AMCNFs) have been fabricated via electrospinning followed by alkaline activation as the negative electrode. The crystal phase, morphological structure for the proposed electrode materials were characterized by x-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Moreover, the electrochemical behaviors were investigated using cyclic voltammetry (CV), galvanostatic charge and discharge (GCD) and electrochemical impedance spectroscopy (EIS) measurements. Compared to the neat CNFs and the pristine NiCo2O4, the NiCo2O4@CNFs hybrid electrodes showed better electrochemical performance and achieved a high specific capacitance up to 649 F g−1 at a current density of 3 A g−1. The optimized NiCo2O4@CNFs//AMCNFs asymmetric device achieved a high energy density of 38.5 Wh kg−1 with a power density of 1.6 kW kg−1 and possessed excellent recyclability with 93.1% capacitance retention over 6000 charging/discharging cycles. Overall, the proposed study introduces a facile strategy for the robust design of hybrid structured as effective nanomaterials based electrode for high-performance electrochemical supercapacitors.