Poly(ε‐caprolactone‐co‐ε‐caprolactam) was synthesized through ring‐opening copolymerization of ε‐caprolactone (CLO) and ε‐caprolactam (CLA) catalyzed by ethyl magnesium bromide (Et‐MgBr) or sodium ε‐caprolactam (CLA‐Na). Varied ester contents were achieved from 0%‐100 mol%. Et‐MgBr enabled the copolymerization with high yield over 95%. Thermal properties vary with different ester contents. With the increasing CLO content, the onset decomposition temperature (273.36 oC to 240.97 oC) and glass transition temperature (52.1 oC to ‐56.3 oC) gradually decreased. The research of melting behavior of resultant PEAs through DSC and theoretical calculation indicated a eutectic temperature of 46.6 oC. The mechanical properties of obtained copolymers were systematically investigated. The enhance of CLO incorporation led to the decrease in tensile strength (9.88‐70.99 MPa) and Young's Modulus (19.18‐690.03 MPa). Copolymer with CLO incorporation of 70 mol% exhibited a eutectic temperature of 46.6 oC, and enabled the high elongation at break (658 %) and enhanced impact strength (138.5 KJ/m2).This article is protected by copyright. All rights reserved.