A unique hybrid binder system based on polyacrylic acid (PAA) and polyacrylamide (PAM) was designed for lithium–sulfur batteries. It is found that the hydrophilic PAM possesses suitable swelling properties and favorable interface reaction kinetics. Moreover, the strong chemical adsorption and hydrogen bond interaction of polar functional groups mainly from PAA confine the out-diffusion of polysulfides and decrease byproduct deposition on the electrode. Electrochemical test results demonstrate that sulfur cathodes equipped with the PAM–PAA binder possess higher reversible capacity, lower charge transfer resistance, and better cycle and rate performances in contrast to conventional PVDF cathodes.