Abstract: Enediyne compounds with chiral amino acid ester groups were synthesized and used as monomers to synthesize chiral polymers. When heated or shined with ultraviolet light, the enediyne compounds undergo Bergman cyclization reaction with diradical intermediates, forming chiral polymers through the coupling reaction of these diradicals. The Bergman cyclization was confirmed by infrared and nuclear magnetic resonance spectroscopy. Gel permeation chromatography results showed that high molecular mass polymers were formed. The main chain chirality of these polymers was further confirmed by circular dichroism analysis.