Fe and P co-doped WO2 nano-polygonal pyramid (Fe-P/WO2), as a precious-metal-free electrode catalyst for hydrogen evolution reaction (HER), was successfully synthesized by a novel organic-inorganic hybridization method. The obtained Fe-P/WO2 composite possesses stable high HER catalytic performance. The over potential (eta(10)) and Tafel slope of the sample Fe-P/WO2 were only 48 mV and 19 mV.dec(-1) higher than those of commercial Pt/C catalyst, respectively. The excellent HER catalytic activity of Fe-P/WO2 composite is due to the synergetic catalytic effect between WO2 and the doped heterogeneous medium.