Towards finding the low-cost electrocatalyst with high catalytic properties to replace the noble metal in use of electrochemical hydrogen evolution reaction (HER) of total water splitting is appropriate to approach the green, sustainable energy supply. Here we synthesized a direct growth of novel copper phosphide peapod nanotube structure for first time coated with amorphous carbon/few-layer graphene from chemically synthesized copper nanowire (Cu NW) at a low temperature of 400 °C by chemical vapor reaction (CVR) process. The as-prepared peapod morphology was evidenced by SEM, TEM and the crystallinity was studied by XRD analysis. Raman and XPS were utilized to evaluate the presence of graphitic carbon at the surface and phases of copper phosphide. This nanostructure exhibits superior electrocatalytic activity by achieving lower overpotential of 287 mV at the current density of 10 mA cm^-2 with low Tafel slope of 72 mV dec^-1 and show excellent stability over 1000 cycles. Besides, the current catalyst prepared from copper save the production cost and could be used as an inexpensive electrocatalyst for all the water splitting systems.