Kinetics of copolymerization of acrylonitrile(AN) with N-vinylpyrrolidone(NVP) initiated by azodiisobutyronitrile(AIBN) was investigated in H2O/dimethyl sulphoxide(DMSO) mixture between 50℃ and 70℃ under N2 atmosphere. The rate of copolymerization and particle size were measured respectively. The kinetic equation 0.651±0.123 1.59±0.35 1.17±0.14of copolymerization system is obtained as Rp ∝ cAIBN cAN cNVP at 60℃. The overall activation energy for copolymerization system was computed as 87.3 kJ.mol-1. Effect of additives of hydroquinone and dioxane on copolymerization was discussed. The polymerization is retarded by hydroquinone and accelerated by dioxane, which confirms the free radical copolymerization of AN with NVP.