Nitrogen-doped carbon nanotubes coated with zinc oxide nanoparticles (ZnO@NCNT) were prepared via a sol–gel route as sulfur encapsulator for lithium/sulfur (Li/S) batteries. The electrochemical properties of the S/ZnO@NCNT composite cathode were evaluated in Li/S batteries. It delivered an initial capacity of 1032 mAh·g⁻¹ at a charge/discharge rate of 0.2C and maintained a reversible capacity of 665 mAh·g⁻¹ after 100 cycles. The coulombic efficiency of the cathode remains unchanged above 99%, showing stable cycling performance. X-ray photoelectron spectroscopy analysis confirmed the formation of S–Zn and S–O bonds in the composite. This indicates that an enhanced cycling and rate capability of the S/ZnO@NCNT composite could be ascribed to advantages of the ZnO@NCNT matrix. In the composite, the active ZnO-rich surfaces offer a high sulfur-bonding capability and the NCNT core acts as a conductive framework providing pathways for ion and electron transport. The as-prepared S/ZnO@NCNT composite is a promising cathode material for Li/S batteries.