A rationally intended electrode material with evolved structure and composition enrichment is highly essential for optimizing the electrochemical performance for the superior charge storage demand of supercapacitors. In this report, we designed and synthesized cobalt-iron phosphide (CFP) hollow/porous nanocubes anchored on cobalt sulfide (CS) nanosheets (NSs) (i.e., CS@CFP) on nickel foam by a hydrothermal process, followed phosphorylation process, as well as a facile wet chemical route. The hollow/porous nanocube (three-dimensional (3D))-on-NS (2D) hybrid array structure and phosphorous incorporation in CS@CFP could significantly enhance the accessibility of electrolyte ions and the electrochemical kinetics of charge as well as redox-active sites.The resultant CS@CFP electrode demonstrated superior charge storage properties with an areal capacity value of 828.6µAhcm