Lithium–sulfur (Li–S) batteries have attracted increasing attention for next-generation energy storage systems with a high energy density and low cost. However, the practical applications have been plagued by the sluggish reaction kinetics and the shuttle effect of lithium polysulfides (LiPSs). Herein, core–shell SiO2@Ti3C2Tx MXene (SiO2@MX) hollow spheres are constructed as multifunctional catalysts to boost the performance of Li–S batteries. The dual-polar and dual-physical properties of SiO2 core and MXene shell provide multiple defense lines to the shuttle effect by chemical and physical confinement to LiPSs. Density functional theory calculations prove that Ti3C2Tx MXene and SiO2 enable the stronger trapping ability of LiPSs and the fast Li2S decomposition process. With this strategy, the robust SiO2@MX/S electrodes deliver superior electrochemical performances, including a high capacity of 1263 mAh g−1, and remarkable cycling stability with an ultralow capacity decay of 0.04% per cycle over 1000 cycles at 1 C. This work highlights the significance of core-shell dual-polar structural sulfur catalysts for practical application in advanced Li–S batteries.