In this study, the role of polyvinyl alcohol (PVA) in eliminating the inhibition phenomenon of modified light-weight carbon black (CB) during the synthesis of polystyrene/modified light-weight carbon black (PS/MLCB) composite particles was examined. It was interesting to note that the polymerization time was largely shortened in the presence of a certain PVA. And the effect of PVA dosage on the polymerization time and the macromorphology of obtained PS/MLCB composite particles were systematically investigated, as well as the correlation between PVA dosage, polymerization time, and MLCB content. In addition, the potential mechanism about the role of PVA in eliminating the inhibition phenomenon of MLCB during the suspension polymerization of styrene was also proposed and analyzed in detail. The PS/MLCB composites particles were studied in terms of surface morphology, thermal stability, and molecular weight. Scanning electron microscopy images of the resulting PS/MLCB composite particles demonstrated that CB was well dispersed in the PS matrix. And the thermal stability of obtained PS/MLCB composite particles was significantly enhanced with the incorporation of MLCB, and increased with the increasing content of MLCB. This synthesis technique brought about a promising future in the large-scale production of black expandable polystyrene. POLYM. ENG. SCI., 2012. (C) 2012 Society of Plastics Engineers