This study aimed to improve the thermal properties of some biopolymers composites. Two aliphatic polyesters were used as matrix, the polylactic acid (PLA) and the polybutylene succinate (PBS). The filler used in the composites was expanded graphite (EG) with three different sizes, 5, 50 and 200 μm. Thermal diffusivities were measured by infrared photothermal radiometry (PTR). Model of effective medium approximation (EMA) was used to study the effect on effective thermal conductivity ke of thermal properties of matrix and fillers, the effect of the interfacial thermal resistance ITR between matrix and fillers or the effect of aspect ratio of fillers. Measurement of particles sizes of fillers before and after preparation process shows the presence of small particles, creating lower thermal conductivities than predicted by EMA model. Filtration of EG before process does not allows to increase ke more than 6% because of mechanical stresses of the process. Finally silane functionalization is used to improve interactions between the fillers and the matrices in order to obtain better thermal conductivities. Mechanical studies on composites are also presented.