Polymer chains, if long enough, are known to undergo bond scission when mechanically stressed. While the mechanochemical response of random coils is well understood, biopolymers and some key synthetic chains adopt well-defined secondary structures such as helices. To understand covalent mechanochemistry in such structures, poly(γ-benzyl glutamates) are prepared while regulating the feed-monomer chirality, producing chains with similar molecular weights and backbone chemistry but different helicities.