Lithium-sulfur batteries (LSBs) have attracted considerable research attention because of their high theoretical capacity and energy density, low cost and environmental friendliness. However, the shuttle effect of lithium polysulfides hinders the commercialization of LSBs. Effectively improving the electrochemical reaction kinetics of the sulfur cathode still represents a significant challenge. Here, a [email protected] composite with a bimodal pore system was designed to electrocatalytically mediate Li/S conversion chemistry. [email protected] presents a large specific surface area (1012 m2 g−1) and two sets of tunnels with pore sizes of 3.63 and 3.47 nm, which efficiently adsorb polysulfides and accelerate the mass transfer of electrolytes. Furthermore, MoN has high intrinsic catalytic activity and enables the rapid conversion of polysulfides. Owing to the synergistic “adsorption-conversion-mass transfer” effect, the electrochemical reaction kinetics are effectively enhanced. Consequently, the [email protected]/S electrode achieves excellent performance with an initial capacity of 1582 mAh g−1 at 0.1C and retains a reversible capacity of 658.4 mAh g−1 after 200 cycles at 1C. The cathode delivers a specific capacity of 475.8 mAh g−1 at a high current density of 5C, with a capacity decay as low as 0.027% per cycle during 1000 cycles. In addition, theoretical calculations reveal that [email protected]/S exhibits low activation energy for Li2S decomposition and effectively inhibits the shuttling of polysulfides. This work provides a new avenue for the development of high-performance LSBs.