We report a novel composite of sulfur loaded in micropore-rich carbon aerogel (CA-S), as cathode of lithium-sulfur battery. Carbon aerogel (CA) is synthesized through phenol-formaldehyde reaction with a low catalyst concentration and carbonization under high temperature, and loaded with sulfur via chemical deposition and heat treatment. The physical properties of the resulting CA and the electrochemical performances of the resulting CA-S are investigated by scanning electron microscopy, thermal gravimetric analysis, Brunauer-Emmett-Teller characterization, electrochemical impedance spectroscopy, and galvanostatic discharge/charge test, with a comparison of a common carbon material, acetylene black (AB), and sulfur loaded in AB (AB-S). It is found that the CA is micropore-rich with micropore volume over 66% of total pore volume, and the CA-S exhibits significantly improved cyclic stability compared with AB-S. The improved performance of CA-S is attributed to the confinement of the micropores in CA to small sulfur allotropes and corresponding lithium sulfides.