The structures of carbon materials greatly affect the electrochemical properties of sulfur/carbon composites for lithium-sulfur (Li-S) batteries. Understanding the effect of carbon structure factors on the electrochemical properties of sulfur/carbon composites helps in rational designing of the cathode material for optimized battery performance. We prepare reduced graphene oxide (RGO), cysteine-modified RGO (RGO-CYS), microwave-expanded graphite oxide (MEGO) and activated-MEGO (aMEGO) with specific surface areas (SSA) of 58–3010 m2 g−1, C/O atomic ratios of 2.41–10.81, pore sizes of 0.9–5.6 nm and pore volumes of 0.14–2.03 cm3 g−1. The electrochemical performance researches S/RGO-CYS > S/RGO > S/MEGO > S/aMEGO when it is listed in the order of their specific capacity, rate capability and cyclic life. And the S/RGO-CYS delivers a high reversible capacity of 455 mA h g−1 at 8 C. The excellent performance of S/RGO-CYS composite is ascribed to the sulfur-containing functional groups of the RGO-CYS, which helps the sulfur dispersion and stabilizes the dissoluble lithium polysulfides. Our results demonstrate that the surface chemistry of carbon materials plays a more important role than the SSA, pore size and pore volume for the electrochemical properties of sulfur/carbon composites for Li-S batteries.