Flexible and free-standing sulphur/(PCNFs-CNT) composite (S@PCNFs-CNT) electrode was successfully prepared by infiltrating sulfur into microporous carbon nanofibers-carbon nanotube (PCNFs-CNT) composite. When used as a cathode material for Li-S batteries, the S@PCNFs-CNT exhibits much better cycle performance and rate performance compared to CNT-free S@PCNFs. It delivers a reversible capacity of 637 mA h g(-1) after 100 cycles at 50 mA g(-1) and a rate capability of 437 mA h g(-1) at 1 A g(-1). The improved electrochemical performance is attributed to synergistic effect of the 3D interconnected structure, the additive of CNT, and the uniform distribution of micropores (<2 nm) in the PCNFs-CNT matrix. Our results indicate the potential suitability of PCNFs-CNT for efficient, free-standing, and high-performance batteries.