Introducing defects into two-dimensional materials can increase the ligand-unsaturated sites, thereby enhancing the redox catalysis of polysulphides. In this study, the selenium defects in the two-dimensional material VSe2 can effectively improve the electrochemical performance of lithium-sulfur batteries. Compared with VSe2, VSe2−x could strongly adsorb polysulfides, catalyze the conversion and accelerate the redox reactions of polysulfides. S/VSe2−x/CNTs cathode with an initial discharge specific capacity of 1457 mAh g−1 at 0.1 C current density and capacity decay rate per cycle of only 0.039% after 800 cycles at 0.5 C, showing excellent cycling stability. In addition, a high areal capacity of 4.35 mAh cm−2 and a reversible capacity of 4.106 mAh cm−2 after 100 cycles at 0.1 C can be achieved with the S/VSe2−x/CNTs cathode with a high areal sulfur loading of 4.5 mg cm−2. The results show that the shuttle effect is effectively suppressed by introducing defects in the two-dimensional transition metal dihalide compounds. Thus, the electrochemical performance of the sulfur electrode for lithium-sulfur batteries is improved. This work is expected to provide a new perspective for the rational design of sulfur host materials for high-performance lithium-sulfur batteries.