Abstract: Both the energy density and cycle stability are still challenges for lithium–sulfur (Li-S) batteries in future practical applications. Usually, light-weight and nonpolar carbon materials are used as the hosts of sulfur, however they struggle on the cycle stability and undermine the volumetric energy density of Li-S batteries. Here, heavy NiCo2O4 nanofibers as carbon-free sulfur immobilizers are introduced to fabricate sulfur-based composites. NiCo2O4 can accelerate the catalytic conversion kinetics of soluble intermediate polysulfides by strong chemical interaction, leading to a good cycle stability of sulfur cathodes. Specifically, the S/NiCo2O4 composite presents a high gravimetric capacity of 1125 mAh g−1 at 0.1 C rate with the composite as active material, and a low fading rate of 0.039% per cycle over 1500 cycles at 1 C rate. In particular, the S/NiCo2O4 composite with the high tap density of 1.66 g cm−3 delivers large volumetric capacity of 1867 mAh cm−3, almost twice that of the conventional S/carbon composites.