Recently, the environmental problem has increased, resulting in a great interest in the biopolymers as substitutes for conventional polymers. However, some properties of biopolymers have to be enhanced to extend the range of use of these materials. A variety of researchers have used the synthesis of copolymers and nanocomposites to improve the properties of biopolymers. The nanocomposite materials are formed by two or more components where one or more of them behave as the matrix in which particles are dispersed in the nanometer range. A large number of studies shows that an addition of a small amount of reinforcing agent can enhance the properties, such as thermal and barrier properties, of those materials. In this study we have investigated the effects of layered double hydroxide (LDH) composed by calcium and aluminum, intercalated with laurate anion, in the thermal properties of poly (L-lactide-ɛ-caprolactone) (PLLCL). The nanocomposite was synthesized by in situ intercalative ring-opening polymerization using 1 % of reinforcement agent and mass ratio of comonomer of 80:20 (L-lactide:ɛ-caporlactone). The X-ray diffraction results showed that the nanocomposite with 1 wt % of reinforcement presented a good dispersion of LDH in the polymeric matrix, and the TGA results revealed that the initial temperature in which degradation began was 236 °C for PLLCL nanocomposite and 218 °C for PLLCL. This enhancement in the properties of nanocomposites can enlarge the range of applications of this material in several areas.