AbstractHere, a new type of anionic hybrid copolymerization is exploited via the concurrent oxa‐Michael addition of ethylene glycol and neopentyl glycol diacrylate and the ring‐opening polymerization of ε‐caprolactone. The hybrid copolymerization process and the resulting copolymers are characterized using nuclear magnetic resonance, size exclusion chromatography, differential scanning calorimetry measurements, and thermogravimetric analysis. The results show that the hybrid copolymerization can proceed smoothly under mild reaction conditions and that the synthesized copolymer contains ester and ether structures in the backbone, possibly endowing the polymers with good hydrophilicity and degradability. More importantly, the composition of the synthesized polymer can be easily adjusted by changing the monomer feed ratio, and the chain crystallization is significantly reduced due to the random copolymeric structure. This hybrid copolymerization reaction provides a new method for synthesizing degradable functional copolymers from commercially available materials. Hence, this polymerization is important not only in polymer chemistry but also in environmental and biomedical engineering.