Polyvinylpyrrolidone (PVP) is used with polyethylene oxide (PEO) as a mixed binder for mechanically milled Li2S. PVP demonstrates its advantage in terms of increasing the capacity of Li2S, but boosts the potential barrier at the beginning of the first charge. It is also revealed that PVP retards the charge-transfer kinetics of Li2S. In Li2S-C prepared by mechanical milling, carbon compensates for the electrochemical insulation of the PVP binder and improves the cycle stability. As a result, the Li2S-C-PVP electrode with 60 wt% Li2S content displays a low potential barrier at the onset of charge and a stable capacity of about 460 mAh g−1 at 0.1 C.