A crucial approach to enhancing the electrochemical performance of lithium-sulfur batteries (LSBs) is to develop a dependable sulfur host material possessing reasonable structure, high electrical conductivity, and exceptional adsorption/catalytic capabilities towards lithium polysulfides (LiPSs). Herein, Co-doped hollow Ti3C2Tx tubes with in-situ grown CNTs as a built-in electron/ion transport network (HTCTs/Co/CNTs) are prepared via electrospinning technique combined with the self-catalyzed growth strategy. The unique hierarchical porous structure of HTCTs/Co/CNTs not only increases the sulfur loading and alleviates the volume expansion, but also effectively suppresses the shuttling effect of LiPSs through the synergism between physical confinement and chemical adsorption. It is revealed that the combination of Ti3C2Tx MXene and metallic Co enhances the LiPSs absorbability and accelerates the catalytic conversion of sulfur species, thereby improving sulfur utilization and electrochemical reversibility. The corresponding cells with HTCTs/Co/CNTs/S cathode retain high capacities of 901.9 mAh g−1 after 100 cycles at 0.2 C and 725.9 mAh g−1 after 500 cycles at 1.0 C. More importantly, a high areal capacity of 4.83 mAh cm−2 is achieved under a high sulfur loading of 5.8 mg cm−2 and a low E/S ratio of 4.3 µL mg−1 after 50 cycles at 0.1 C.