Hollow Co2P nanoflowers (Co2P HNF) are successfully prepared via a one-step, template-free method. Microstructure analysis reveals that Co2P HNF is assembled by nanorods, possesses abundant mesopores and a amorphous carbon shell. Density functional theory calculation and electrochemical measurements demonstrate the high electrical conductivity of Co2P. Benefiting from the unique nanostructures, when employed as electrode material for supercapacitors, Co2P HNF exhibits a high specific capacitance, an outstanding rate capability, and an ultralong cycle stability. Furthermore,. the constructed Co2P HNF//AC ASC yields a high energy density of 30.5 Wh kg-1 at a power density of 850 W kg-1, along with an superior cycling performance (108.0% specific capacitance retained after 10000 cycles at 5 A g-1). These impressive results make Co2P HNF a promising candidate for supercapacitor applications.