As a typical type of layered transition metal dichalcogenides (TMD), MoS2 has a sandwich structure that consists of covalently bonded S–Mo–S trilayers separated by a relatively large van der Waals interaction. This distinct structure makes MoS2 having a momentous applications in the energy storage area. As an anode material, the electrical conductivity of MoS2 is too low and its cycling stability is unsatisfactory for that it is easy to agglomerate in the charge-discharge process. Therefore, preparation of MoS2 composite possessing high electrical conductivity and less volume expansion is of great importance. To solve the issues, we present a facile approach for the synthesis of MoS2/C hollow microspheres by one-pot hydrothermal method. The X-ray diffraction (XRD) result shows that the stack of MoS2 is effectively prevented, and the typical 002 characteristic peak completely disappear indicating that the layer of MoS2 is mono- or few layer. Meanwhile, the high-resolution transmission electron microscopy (HRTEM) shows that as-prepared MoS2/C composite structure is hollow microspheres with porous amorphous carbon nuclear encapsulated by the shell of MoS2. The prepared MoS2/C hollow microspheres exhibit outstanding cycling stability and rate behavior for application as anode material of lithium-ion battery (LIB). Keywords: lithium-ion battery, one-pot hydrothermal method, hollow microspheres. This work is supported by 973 Project of China (2013CB934700).