Copolymers and block-copolymers of ε-caprolactam, α-angelicalactone and polyangelicalactone were first synthesized by the anionic polymerization method. Yields of polymers and rates of their formation decrease with increasing the α-angelicalactone and polyangelicalactone concentration. Physical and mechanical properties of the obtained copolymers are very close to the properties of polycaprolactam. The synthesized block-copolymers are biodegradable in the grey forest soil, and they are completely visually destroyed during 20 weeks. The water extracts of the biodegradation products are nontoxic.