A novel amorphous flower-like molybdenum sulfides@nitrogen doped carbon nanofibers (MoSx@NCNFs) films are successfully synthesized by combining electrospinning, carbonization and a mild hydrothermal process. NCNFs, as a conductive substrate, can accelerate the electron transfer rate and depress the aggregation of MoSx nanoparticles. The resultant amorphous flower-like MoSx on NCNFs exposes abundant S2-/S-2(2-) active edge sites which is of great importance for hydrogen evolution reaction (HER) catalytic performance. Electrochemical measurements demonstrate the superior electrocatalytic activity of MoSx@NCNFs toward HER deriving from the synergistic effect between NCNFs and amorphous MoSx. The overpotential is only 137 mV to reach the current density of 10 mA cm(-2) with a Tafel slope of 41 mV decade(-1) at MoSx@NCNFs. Meanwhile, MoSx@NCNFs exhibits satisfactory long-time stability for HER. Noteworthy, the obtained composites show a free-standing structure which can be directly used as electrode materials. This work provides a feasible way to design promising noble-metal free electrocatalysts in the aspect of energy conversion. (C) 2016 Elsevier Inc. All rights reserved.