The construction of efficient and robust CoP-based hybrid catalysts for the hydrogen evolution reaction (HER) remains challenging. In this work, a facile thermal decomposition method has been used to synthesize CoP nanorods (NRs) in situ grown on graphene oxide co-doped with nitrogen and sulfur (CoP/ NSGO) as a high activity and stability hybrid catalyst for the HER. The catalysts were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and N-2 sorption. The as-synthesized CoP/NSGO catalyst exhibited much higher HER performance than CoP/NGO and CoP/GO catalysts, indicating the positive role of N, S co doping into the graphene frame. The formation of pyridinic N and pyrrolic N species as well as thiophene S species, which acted as novel active centers and benefited the suitable chemisorption of intermediates for catalyzing HER, improved the catalytic activity. Our current research indicates that both nitrogen and sulfur atoms played an important role in enhancing the HER performance for CoP-based catalysts. (C) 2016 Published by Elsevier Ltd.