Herein, N-Ti3C2@CNT microspheres are suc?cessfully synthesized by the simple spray drying method. In the preparation process, HCl-treated melamine (HTM) is selected as the sources of carbon and nitrogen. It not only realizes in situ growth of CNTs on the surface of MXene nanosheets with the catalysis of Ni, but also introduces effcient N-doping in both MXene and CNTs. Within the microsphere, MXene nanosheets interconnect with CNTs to form porous and conductive network. In addition, N-doped MXene and CNTs can provide strong chemical immobili?zation for polysulfides and effectively entrap them within the porous microspheres. Above-mentioned merits enable N-Ti3C2@CNT microspheres to be ideal sulfur host. When used in lithium–sulfur (Li–S) battery, the N-Ti3C2@CNT microspheres/S cathode delivers initial specific capac?ity of 927 mAh g?1 at 1 C and retains high capacity of 775 mAh g?1 after 1000 cycles with extremely low fading rate (FR) of 0.016% per cycle. Furthermore, the cathode still shows high cycling stability at high C-rate of 4 C (capacity of 647 mAh g?1 after 650 cycles, FR 0.027%) and high sulfur loading of 3 and 6 mg cm?2 for Li–S batteries.