Using the wide-angle X-ray scattering method, the degree of crystallinity of suspension copolymers and terpolymers of acrylonitrile (AN) and divinylbenzene (DVB) were determined. Copolymers with various degrees of cross-linking (5%-50% DVB) were prepared in the presence of thermodynamically different solvents added in order to obtain porous structure. It was found that copolymers with a degree of cross-linking of 0.1% DVB have a crystallinity index below 0.2, although the crystallinity index of PAN obtained under the same conditions is 0.5. Owing to the solvation conditions, even in copolymers with a degree of cross-linking of 20% DVB, ordered regions occur, and dilution of the polymerization mixture with poor solvents cause a decrease in the degree of crystallinity of these copolymers. Terpolymers AN, butyl acrylate (BA) or vinyl acetate (VA) have less ordered structure for the same amount of DVB. Methacrylonitrile and DVB copolymers obtained under the same conditions as AN and DVB are amorphous.