A unique S@TiO2/Ti2C nanoarchitecture was firstly synthesized as cathodes for lithium-sulfur batteries, in which TiO2 hollow nanospheres encapsulating sulfur were embedded into MXene Ti2C interlayers. The as-prepared S@TiO2/Ti2C composites exhibited an excellent electrochemical performance. The initial discharge specific capacity was 1408.6 mAh g−1 at 0.2C with a high sulfur content of 78.4 wt.%. At a high current rate of 2C and 5C, the batteries still maintained a capacity up to 464.0 and 227.3 mAh g−1 after 200 cycles, respectively. The enhanced electrochemical properties of S@TiO2/Ti2C composites was attributed mainly to the synergistic effect between the encapsulation and adsorption of TiO2 for active sulfur, and the conductivity and relieving the volumetric expansion of Ti2C for cathode materials. This structure strategy was an attractive route for restraining the shuttle effect and improving the rate capability of sulfur cathodes for lithium-sulfur batteries.