The morphology and structure of the electrocatalysts are important factors affecting their performance for electrochemical splitting water into hydrogen. Herein, the urchin-like CoP nanomaterials with the large specific surface area (SSA) were fabricated through the solvothermal process and the solid-gas reaction for hydrogen evolution reaction (HER). The resulting CoP nanomaterial with a diameter of approximately 4 mu m was assembled by the nanowires with a length of about 10 nm. The excellent performance is accessible for HER with a small overpotential of 130 mV and a low Tafel slope of 52 mV/decade in a 0.5 M H2SO4 aqueous solution. Especially, the resulting urchin-like CoP nanomaterials with a large SSA and electric double-layer capacitance lower the electrochemical impedance and accelerate the electron transfer, endowing the excellent performance for HER process.