An efficient electrocatalyst for hydrogen evolution has been developed based upon in situ reduction of MoS2 on ordered mesoporous carbon nanospheres (MoS2/MCNs). The properties of MoS2/MCNs were characterised by scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. Polarisation curves and electrochemical impedance measurements were obtained for MoS2/MCNs modified glassy carbon electrodes. The MoS2/MCNs exhibit high catalytic activity for hydrogen evolution with a low overpotential and a very high current density. A theory outlining the origins of the Tafel slope for a Volmer-Heyrovsky (rate determining step) mechanism of hydrogen evolution at MoS2 catalytic edge sites is presented.