Hollow carbon nanofiber@nitrogen-doped porous carbon (HCNF@NPC) coaxial-cable structure composite, which is carbonized from HCNF@polydopamine, is prepared as an improved high conductive carbon matrix for encapsulating sulfur as a composite cathode material for lithium–sulfur batteries. The prepared HCNF@NPC–S composite with high sulfur content of approximately 80 wt% shows an obvious coaxial-cable structure with an NPC layer coating on the surface of the linear HCNFs along the length and sulfur homogeneously distributes in the coating layer. This material exhibits much better electrochemical performance than the HCNF–S composite, delivers initial discharge capacity of 982 mAh g−1 and maintains a high capacity retention rate of 63% after 200 cycles at a high current density of 837.5 mA g−1. The signiﬁcantly enhanced electrochemical performance of the HCNF@NPC–S composite is attributed to the unique coaxial-cable structure, in which the linear HCNF core provides electronic conduction pathways and works as mechanical support, and the NPC shell with nitrogen-doped and porous structure can trap sulfur/polysulfides and provide Li+ conductive pathways.