Synthesis and radical polymerization of a proline-substituted acrylamide, N-methacryloyl-L-proline methyl ester (A-P-M) were carried out. The isomerization of A-P-M between s-cis and a-trans forms of A-P-M was analyzed by H-1 NMR spectroscopy and molecular dynamics simulation, and the effect of the cis-trans isomerization on the radical polymerization of A-P-M was examined. The content of s-cis form of h-P-M increased with the NMR measuring temperature. The radical polymerization of A-P-M at higher temperature afforded the polymer with a higher s-cis content and a lower absolute value of specific rotation. It was suggested that the s-cis/s-trans ratio and the tacticity of the polymer affected the optical properties.