The polymerization of gamma-methylglutamate N-carboxyanhydride (MeGluNCA) using Schiffs base/aluminum methoxide or isopropoxide (HAPENAlOMe or HAPENAlO(i)Pr) at ambient temperature is reported. A range of polymers have been synthesized by varying the nature of the solvent and initiator concentrations. The initiation is shown to proceed through complexation of the nitrogen of an NCA to the aluminum atom. The coordinated NCA then undergoes a nucleophilic attack by the alkoxide with loss of carbon dioxide. Chain propagation takes place by nucleophilic attack of the bound amido onto C(5)=O of an NCA. The presence of a methoxy or isopropoxy ester group at the initiated chain end has been confirmed by MALDI-TOF analysis.