The mesoporous MoO2 nanospheres are successfully synthesized by hydrothermal reduction process that is feasible and environmentally friendly. The as-prepared MoO2 nanospheres are used as efficient sulfur matrix in lithium‑sulfur battery to improve its electrochemical performance. Higher capacity retention and better rate performance can be achieved, compared with the acetylene black/sulfur cathode, which can be attributed to the conductive MoO2 nanospheres uniformly dispersed in sulfur, enhancing electron transfer and reducing interfacial impedance. The MoO2/S composite cathode exhibit a discharge capacity of 1144mAhg −1 at a high rate of 2.2mAcm−2 in the first cycle, and maintained 780mAhg−1 after 200cycles. Furthermore, even under a rate of 4.4mAcm−2, it still maintained a substantial capacity of 635mAhg−1. It is demonstrated that the addition of mesoporous MoO2 improving electrochemical performances of the batteries, which effectively slowed down the dissolution of polysulfides in the electrolyte and shorten the diffusion distances for lithium ions on interaction during the charge-discharge processes.