We have investigated the chemical bonding interaction of S in a CTAB (cetyltrimethylammonium bromide, CH3(CH2)15N+(CH3)3Br-)-modified sulfur-graphene oxide (S-GO) nanocomposite used as the cathode material for Li/S cells by S K-edge X-ray absorption spectroscopy (XAS). The results show that the introduction of CTAB to the S-GO nanocomposite and changes in the synthesis recipe including alteration of the S precursor ratios and the sequence of mixing ingredients lead to the formation of different S species. CTAB modifies the cathode materials through bonding with Na2Sx in the precursor solution, which is subsequently converted to C-S bonds during the heat treatment at 155 °C. Moreover, GO bonds with CTAB and acts as the nucleation center for S precipitation. All these interactions among S, CTAB, and GO help to immobilize the sulfur in the cathode and may be responsible for the enhanced cell cycle life of CTAB-S-GO nanocomposite-based Li/S cells.