Lithium-sulfur (Li-S) batteries can provide far higher energy density than currently commercialized lithium ion batteries, but challenges remain before it they are used in practice. One of the challenges is the shuttle effect that originates from soluble intermediates, like lithium polysulfides. To address this issue, we report a novel laminar composite, N,O-carboxymethyl chitosan-reduced graphene oxide (CC-rGO), which is manufactured via the self-assembly of CC onto GO and subsequent reduction of GO under an extreme condition of 1 Pa and .50 .C. The synthesized laminar CC-rGO composite is mixed with acetylene black (AB) and coated on a commercial polypropylene (PP) membrane, resulting in a separator (CC-rGO/AB/PP) that can not only completely suppress the polysulfides penetration, but also can accelerate the lithium ion transportation, providing a Li-S battery with excellent cyclic stability and rate capability. As confirmed by theoretic simulations, this unique feature of CC-rGO is attributed to its strong repulsive interaction to polysulfide anions and its benefit for fast lithium ion transportation through the paths paved by the heteroatoms in CC.