Although lithium–sulfur batteries (LSBs) possess a high theoretical specific capacity and energy density, the inherent problems including sluggish sulfur conversion kinetics and the shuttling of soluble lithium polysulfides (LiPSs) have severely hindered the development of LSBs. Herein, cobalt selenide (CoSe₂) polyhedrons anchored on few-layer TiSe₂-C nanosheets derived from Ti₃C₂T_x MXenes (CoSe₂@TiSe₂-C) are reported for the first time. The dual-conductive CoSe₂@TiSe₂-C heterostructures can accelerate the conversion reaction from liquid LiPSs to solid Li₂S and promote Li₂S dissociation process through high conductivity and lowered reaction energy barriers for promoting overall sulfur redox kinetics, especially under high sulfur loadings and lean electrolyte. Electrochemical analysis and density functional theory calculation results clearly reveal the catalytic mechanisms of the CoSe₂@TiSe₂-C heterostructures from the electronic structure and atomic level. As a result, the cell with CoSe₂@TiSe₂-C interlayer maintains a superior cycling performance with 842.4 mAh g⁻¹ and a low-capacity decay of 0.031% per cycle over 800 cycles at 1.0 C under a sulfur loading of 2.5 mg cm⁻². More encouragingly, it with a high sulfur loading of ≈7.0 mg cm⁻² still harvests a high areal capacity of ≈6.25 mAh cm⁻² under lean electrolyte (electrolyte/sulfur, E/S ≈ 4.5 µL mg⁻¹) after 50 cycles at 0.05 C.