AbstractAn alternating high‐molecular‐weight polymer of L‐valine and L‐lactic acid was synthesized in the solid state. Results from circular dichroism (CD) and nuclear magnetic resonance (NMR) spectra indicate that these polymers are helical in helicogenic solvents such as chloroform and trifluoroethanol (TFE). The conformational analysis is extended to include semi‐empirical energy calculations for alternating α‐amino and α‐hydroxy acid polymers. Preliminary calculations based on depsipeptides from L‐alanine and L‐lactic