Anionic copolymerizations of acrylonitrile (monomer 1) with β-propiolactone (monomer 2) and the structures of the resulting copolymers were studied. The copolymerization with sodium cyanide in N,N-dimethylformamide gave copolymers of the structure I containing acid anhydride linkage in the molecular chains, with the monomer reactivity ratios, r1 = 1.20, r2 = 0.00. The copolymerization with potassium hydroxide gave either copolymers of the structure II (r1 = 0.00, r2 = 3.64 at 30°C; r1 = 0.00, r2 = 5.00 at 40°C) in N,N-dimethylformamide or only β-propiolactone homopolymer in toluene.