In this paper, the salt effect of lithium bromide (LiBr) on the dimethyl formamid (DMF) solution polymerization of acrylonitrile was studied. From the experimental data, we proposed a possible mechanism and derived its rate expression to determine the kinetic parameters for this system. The results show that the values ofkv/ktr(1.984∼79.365) andkt/k2tr(3.311×l02∼3.156×l05sec·mole/1) of the DMF‐LiBr solution polymerization of acrylonitrile are larger than those of the DMF‐LiCl solution polymerization of acrylonitrile shown by Bamford and others. These results can be explained by the basicity of salt and the dissociation of polyacrylonitrile in the DMF‐LiBr solution.