Copoly(ester amide)s, abbreviated as PVGAn, have been prepared by random copolymerization of 1-amino-1-deoxy-2,3,4-tri-O-methyl-5-O-[(pentachlorophenoxy)succinyl]-L-arabinitol hydrochloride and 5-amino-1-O-[(pentachlorophenoxy)glutaryl] pentanol hydrochloride by the active ester polycondensation method. The molar ratios of the two comonomers in the feed varied from 1/99 to 50/50. The two monomeric units are randomly distributed within the copolymers, as assessed by NMR analysis, and the degree of randomness and average sequence lengths of the different copoly(ester amide)s have been experimentally determined. Thermal properties depend on the copoly(ester amide) composition, since it was found that the melting and the decomposition temperatures decreased as the molar fraction of carbohydrate-based monomer unit increased, whereas the glass-transition temperature increased in parallel.