MoS2-decorated coaxial nanocable carbon aerogel (MoS2/CNCA) has been successfully prepared by phenol aldehyde reaction on the substrate of multi-walled carbon nanotube with catalysis of ammonium molybdate followed pyroprocessing with sulfur. The as-prepared samples were characterized by transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis, X-ray powder diffraction, and X-ray photoelectron spectroscopy. The MoS2-decorated carbon aerogel (CA) with carbon nanotube as fine wire presents narrow distribution of pore size, interconnected structure and high conductance. The MoS2/CNCA/S composites exhibit improved electrochemical performances as cathode of lithium-sulfur batteries. Especially, the MoS2-8/CNCA/S composite delivers a discharge capacity of 1343 mAh g−1 at 0.2 C with the capacity retention of 81% after 200 cycles. Even at 5 C, the electrode presents high discharge capacity of 723 mAh g−1. These improved results can be attributed to the contribution of entangled network as electronic conductive channel, large surface area, small pore size and special anchoring action of molybdenum disulfide.