Synthesis of amino acid or peptide-bearing polymers with controlled microstructures is still a long-going challenge in polymer chemistry in contrast to natural biopolymers with exactly controlled microstructures like proteins and DNA. Here, a series of new glycine-substituted cyclooctenes monomers were designed and synthesized. Ring-opening metathesis polymerizations (ROMP) of all 3-substituted monomers with Grubbs second-generation catalyst afford glycine-bearing polymers with high head-to-tail regioregularity and high trans-stereoregularity, whereas ROMP of 5-substituted monomers is neither regio- nor stereoselective.