The acrylonitrile copolymer/dimethylformamide (DMF) solutions were prepared to investigate the gelation behavior and critical gel concentration (c＊). Gelation is rapidly progressed with the increase of molecular weight of copolymer, but significantly delayed with supercooling temperature and comonomer contents. The c＊ behavior showed contrary trend against gelation behavior. In dynamic viscoelastic test, two glass-transition region were observed in film obtained from gelled solution whereas one glass-transition in film obtained from true solution. This result supports the idea that an ordered junction zone is formed by the dipole-dipole interaction of intermolecularly neighboring stereo-regular parts of atactic acrylonitrile copolymer chains due to a nucleation process in the solution.