Carbon nanofibers (CNFs) was produced as load matrix and reactor based on the electrospinning technology and carbonization process, which is used as nanoreactor for the grouth and regulation of molybdenum disulfide (MoS2) nanosheets. Taking the advantage of high catalytic activity of MoS2 nanosheets, high specific surface area, good stability, and high electrical conductivity of carbon nanofibers (CNFs), we have investigated the electrocatalytic activity of MoS2/CNFs with different morphologies and structures for hydrogen evolution reaction (HER). A variety of analytical techniques were used to investigate the prepared hybrid nanomaterials. Meanwhile. MoSJCNFs hybrid materials were used to study the electrocatalytic activity, and it is found that the MoS2/CNFs-10 with core-shell structure for HER has the best electrocatalytic activity with onset potential of 220 niV and Tafel slope of 110 mV center dot dec(-1).