According to kinetic mechanisms, liquid phase polymerization and solid phase polymerization are different in acrylonitrile (AN) polymerization, and so the relationship between the contribution ratio and molecular weight distribution (MWD) was obtained through theoretic analysis. The precipitation homopolymerization of AN was carried out in a mixture solution of dimethyl sulfoxide (DMSO) and water at 50~65oC using α,α’-azobisisobutyronitrile as an initiator. The contribution ratio decreased and approached 0; the MWD also decreased and approached 2 with the increase of the H2O/DMSO ratio from 10/90 to 90/10. The experimental data were found to coincide well with the theoretical equation derived from the mechanisms