A series of aliphatic poly(ester amide)s derived from 1,6-hexanediol, glycine, and diacids with a variable number of methylenes (from 2 to 8) have been synthesized and characterized. Infrared spectroscopy shows that the studied polymers present a unique kind of hydrogen bond that is established between their amide groups. Thermal properties as melting, glass transition, and decomposition temperatures are reported. The data indicate that all the polymers are highly crystalline. Thus, different kinds of spherulites (positive and/or negative) were obtained depending on the preparation conditions and on the polymer samples. Moreover, all the polymers crystallized from dilute diol solutions as ribbonlike crystals where a regular folding habit and a single hydrogen bond direction could be deduced. A test of enzymatic hydrolysis was employed to assess the potential biodegradability of these polymers.