Formaldehyde, resorcinol, and sodium acetate were used to synthesize the carbon aerogels by ambient pressure drying. The effect of the ratio of resorcinol and sodium acetate for carbon aerogels was researched by scanning electron microscope and Brunauer-Emmett-Teller characterizations. Then the carbon aerogels were applied in synthesizing sulfur/carbon aerogel composites through a melting method, the specific capacity and cycle performance of lithium/sulfur batteries that adopted the prepared composites as cathodes were measured by galvanostatic discharge–charge. X-ray diffraction, conductivity measurement, cyclic voltammetry, and electrochemical impedance spectra tests were also carried out to help explain the electrochemical performance. Finally, the carbon aerogel with the best properties was chosen for the comparative study of replacement of water by acetone as solvent in the preparation of carbon aerogels. According to our study, the carbon aerogel prepared by ambient pressure drying with high electrical conductivity, controllable pore structure, and high specific surface area was proposed to be used for lithium/sulfur batteries, and the key factors to the performance of carbon aerogel/sulfur composites were discussed.