An alternating poly(ester amide) constituted by 6-amino-1-hexanol and glutaric units has been synthesized by different ways involving solution or thermal polycondensation. Results of the synthesis are compared, and the occurrence of a thermal degradation through imide ring formation is demonstrated. Hydrolytic and enzymatic degradation of the new polymer has been evaluated by means of weight loss measures and changes in intrinsic viscosity or by analysis of NMR spectra. Thermal properties and crystallization kinetics have also been studied. Crystalline structure has been investigated by X-ray fiber diffraction and electron microscopy of lamellar single crystals. Results indicate that polymorphism exists involving packing modes similar to those found on aliphatic polyamides.