Lithium-sulfur batteries are regarded as promising candidates for energy storage devices due to their high theoretical energy density. Various approaches are proposed to break through the obstacles that are preventing Li-S batteries from realizing practical application. Recently, the importance of the strong chemical interaction between polar materials and polysulfides is recognized by researchers to improve the performance of Li-S batteries, especially with respect to the shuttle effect. Polar materials, unlike nonpolar materials, exhibit strong interactions with polysulfides without any modification or doping because of their intrinsic polarity, absorbing the polar polysulfides and thus suppressing the notorious shuttle effect. The recent advances on polar materials for Li-S batteries are reviewed here, especially the chemical polar-polar interaction effects toward immobilizing dissolved polysulfides, and the relationship between the intrinsic properties of the polar materials and the electrochemical performance of the Li-S batteries are discussed. Polar materials, including polar inorganics in the cathode and polar organics as binder for the Li-S batteries are respectively described. Finally, future directions and prospects for the polar materials used in Li-S batteries are also proposed.