AbstractPoly(Glu(OBzl)‐Gly)n, poly(Glu‐Gly)n, poly(Gly)‐(Glu(OBzl)‐Gly), and poly(Gly‐Glu‐Gly) were synthesized from the pentachlorophenyl esters of the sequential monomer. Both of the polymers containing free glumatic‐acid residues are soluble in water, as is the lower molecular weight fraction of the polytripeptides with the benzyl ester in place. Circular dichroism studies and infrared dichroism studies suggest that the 21 helix is favored for the polydipeptide with removal of the benzyl ester reducing the conformational integrity. The polytripeptide showed evidence of 31 helix in addition to the 21 form, depending on solvent. A rationale for the conformations observed is developed based on the bulkiness of the side‐chain residues and conformational stabilization, in certain cases, by hydrophobic interactions between the benzyl ester groups.