Binder, one of the most important battery components, plays a critical role in lithium–sulfur batteries. Poly(vinylidene difluoride) (PVDF), a commonly used binder in lithium–sulfur batteries, does not have a strong affinity to the intermediate polysulfides, however, leading to fast capacity fading with electrochemical cycling. Herein, copolymers of vinylidene difluoride with other monomers are used as multi-functional binders to enhance the electrochemical performance of lithium–sulfur batteries. Compared to the PVDF, the copolymer, poly(vinylidene difluoride-trifluoroethylene) (P(VDF-TRFE)) binder exhibits higher adhesion strength, less porosity, and stronger chemical interaction with polysulfides, which helps to keep the polysulfides within the cathode region, thereby improving the electrochemical performance of the lithium–sulfur battery. As a result, sulfur electrode with P(VDF-TRFE) binder delivered a high capacity of 801mAhg−1 at 0.2C after 100 cycles, which is nearly 80% higher capacity than the corresponding sulfur cathode with PVDF binder.