Aliphatic polyesters have attracted industrial attention as environmentally degradable thermoplastics to be used for a wide range of applications. Besides intensive studies on the biodegradability of aliphatic polyesters, understanding of the thermal stability has importance for processing, application, and recycling. The details of thermal degradation processes of five types of aliphatic polyesters; namely, poly(L-lactide), poly(3-hydroxybutyric acid), poly(4-hydroxybutyric acid), poly(delta-valerolactone), and poly(epsilon-caprolactone), were investigated by means of several thermoanalytical techniques under both isothermal and non-isothermal conditions. In this feature article, the thermal degradation behaviors of aliphatic polyesters with different numbers of carbon atoms in the main chain of the monomeric unit are reviewed. In addition, the effects of chain-end structure and residual metal compounds on the thermal degradation processes of aliphatic polyesters consisting of hydroxyalkanoic acid monomeric units are presented. Schemes of thermal degradation reaction of poly(hydroxyalkanoic acid)s.