We present a facile method of growing MoSe2 on carbon nanofibers (CNFs) via chemical vapor deposition (CVD). Polyacrylonitrile (PAN) was electrospun into nanofibrous mats and graphitized to form CNFs. Subsequent selenization of MoO3 in a CVD system on the surface of the CNFs produced MoSe2/CNFs hybrid. Scanning and transmission electron microscope (SEM and TEM) images revealed large-area MoSe2 nanosheets attached to the CNFs and indicated that the synthesized MoSe2/CNFs hybrids were highly crystalline. Such a structure should increase the surface area and maximally expose the MoSe2 edges, which may boost catalytic activity. The MoSe2/CNFs hybrid was directly used as working electrode for hydrogen evolution reaction (HER) and exhibited significantly enhanced catalytic activity. The onset potential, the over-potential at a current density of 10 mA cm(-2), and Tafel slope of the MoSe2/CNFs hybrid were -69 mV, -219 mV, and 107 mV decade(-1), respectively. The results suggest that the MoSe2/CNFs hybrid can serve as effective and promising catalyst for HER.