Development of high-efficiency electrocatalysts for a hydrogen evolution reaction (HER) is of great importance for the sustainable production of hydrogen that is necessary to relieve the energy crisis. Construction of a non-noble metal organic-inorganic hybrid structure with excellent HER activity is the key issue in electro-catalytic fields. Here, we demonstrate a facile synthetic route to prepare a flower-like MoS2/CNFs hybrid structure with a high concentration of active edges sites using a hydrothermal method. The hybrid structure exhibits brilliant electro-catalytic performance in the HER process with an overpotential of 45 mV and the lower Tafel slope of 58 mV dec(-1), as well as a remarkable durability. The excellent HER activity of the MoS2/CNFs hybrid structure is attributed to the high number of exposed active edges sites, high conductivity of carbon nanofibers (CNFs) and the high surface area of the CNFs mat.