NiCoP hollow microspheres were synthesized by a solvothermal route. The experimental results showed that the NiCoP was composed of large quantities of hollow spheres, indicating the mesoporous materials. In addition, the electrochemical performance of NiCoP hollow spheres were also examined as the anode materials for lithium ion batteries. The results indicated that the initial discharge capacity of the NiCoP was as high as 980mAhg−1 and its discharge capacity still kept at 325mAhg−1 after the 100th cycle, which may be that the large surface area was conducive to the Li+ insertion/extraction during the charge–discharge process.