Redox polymerization of acrylonitrile (AN) with ethyl acrylate (EA) and fumaronitrile (FN), as comonomer and termonomer respectively, were carried out using sodium bisulfite (SBS) and potassium persulphate (KPS) as initiators at 40°C. The actual composition of monomers in copolymers and terpolymers has been characterized by gas chromatography (GC). The effects of EA and FN on the glass transition temperature (Tg) and stabilization temperature have been studied by Differential Scanning Calorimetry (DSC). The degradation behaviour and char yield were obtained by thermogravimetric analysis. Meanwhile, incorporation of 10 mol% of EA in homoPAN system was found to greatly reduce Tg to 66°C as compared to that of the homoPAN (Tg=105°C). The initial cyclization temperature (Ti) was found to be higher (264°C) in comparison to that of homoPAN (246°C). In addition, the incorporation of EA was also shown to reduce the char yield of copolymer to 40%. When FN was incorporated as termonomer, the char yield of poly(AN/EA/ FN) 90/4/6 increased up to 44% after the heat treatment with the lowest Ti (241°C).