Recently, Li-S batteries with a high theoretical specific energy have attracted significant attention. However, their practical application is still seriously hindered by the shuttling effect of lithium polysulfides (LiPSs) in the Li-S batteries system. Introducing anchoring materials into the cathode or separator, which can strongly attract LiPSs because of advisable binding energies, has been demonstrated as an effective strategy to alleviate the shuttling effect for achieving the excellent cycling performance of Li-S batteries. In this work, the complete mechanistic understanding of the interaction between non-metallic monolayer materials (N-MMLMs, including Graphene, BN, C2N and C3N4) and LiPSs is given in detail with the aid of density functional theory. The calculation results show that N-MMLM can combine the chemical interaction and the physical entrapment of sulfur species to suppress the shuttling effect. C3N4 and C2N are predicted to trap LiPSs via stronger interfacial interaction and alleviate the interactions between LiPSs and solvents as well as the consequent dissolution. The strong anchoring effect of C3N4/C2N comes from the bonding of Li-N/C-S and charge transfer. Further charge transfer study reveals that the C3N4/C2N can serve as an electrocatalyst, which effectively accelerates the kinetics of LiPSs redox reactions. (C) 2017 Elsevier B.V. All rights reserved.