Growing environmental concerns have led to the development of alternative biodegradable polymers with properties comparable to the conventional poly(ethylene), poly(propylene) or poly(ethylene terephthalate). In this paper the thermal degradation of poly(F-caprolactone) (PCL) and poly(L-lactide) (PLLA) melts was investigated by rheometry and thermogravimetry under different temperatures and inert atmosphere. The chain scission process was modeled to explain the phenomenon. The analysis suggests that PLLA is degraded by an unzipping depolymerization process from the hydroxyl end of the polymer chains. In contrast, the thermal degradation behavior of PCL was very complex because various reactions occurred concurrently: post-polymerization, loss of structural regularities and random chain scissions.