A new reaction model for dichloropropanol (DCP) synthesis from glycerol chlorination is proposed based on the models reported by Tesser et al. (2007) and Luo et al. (2009). Two reaction steps, glycerol to glycerol-1-acetate and α-MCP to 3-chloropropandiol-1-acetate, were defined as reversible reactions and other reaction steps were defined as irreversible processes. Using the experimental data reported by Luo et al. (2009), the values predicted in this study were compared with the previous model reported by Luo et al. (2009) using both the average absolute deviation (AAD) and root mean square deviation (RMSD). The AAD and RMSD of the new model were 31% and 33% lower than that of the existing one, respectively. Overall, the proposed model for glycerol chlorination is superior to the previous model.