AbstractTransition metal polysulfides MSx (x > 2) have attracted much attention because of their high theoretical capacities as electrode materials for lithium batteries. Among them, VS4 has a linear chain structure in which van der Walls forces exist between chains. Previous reports found lithium ions can be intercalated into VS4 in the discharge, and elemental V and Li2S are formed when discharged to low voltage (e.g., <1.0 V vs Li/Li+). In this study is found that bis(trifluoromethanesulfonyl)imide (TFSI−) anions can be intercalated into VS4 when charged to 3.0 V or above after discharged to 1.8 V in rechargeable lithium battery, triggering sulfur evolution. To improve its cycling reversibility diphenyl disulfide (DPDS) is used as a sulfur receptor in the composite electrode consisting of nanoscaled VS4 particles and carbon nanotubes (CNTs). In the charge, sulfur atoms are transferred from VS4 to DPDS forming diphenyl trisulfide (DPTS). This strategy enables improved capacity retention and material utilization. The electrode shows a reversible capacity of 130.7 mAh g−1 after 300 cycles at the current density of 240 mA g−1.