ZnS/C nanoparticles with core/shell structure are prepared by a simple solvothermal process followed by an annealing process. The core consists of a quite amount of ultrasmall ZnS nanocrystals (∼10nm) dispersing in in situ formed carbon matrix, which is covered by an outer carbon shell with ∼4nm thickness. The nano-sized ZnS crystals effectively shorten the lithium ion diffusion paths, while the uniform carbon shell, together with the inner amorphous carbon matrix not only provide fast electron conduction, but also act as a buffer matrix to accommodate volume change occurring on electrochemical cycling. Such hierarchical-type microstructure is beneficial concerning electrochemical performance of the proposed composite. When evaluated as an anode material for rechargeable lithium ion batteries, the ZnS/C nanocomposite shows a high specific capacity of 741mAhg−1 at a current density of 0.1Ag−1 after 300 cycles. Even at 5Ag−1, a high reversible capacity of 538mAhg−1 can be still achieved. The lithium diffusion coefficient of ZnS/C electrode is estimated as 6.1×10−11 cm2 s−1, contributing to the excellent rate performance of the material.