Poly(propylene adipate) (PPA) and poly(propylene isophthalate/adipate) (PPI–PPA) random copolymers of various compositions were synthesized in bulk and characterized in terms of chemical structure and molecular weight. Furthermore, the thermal behavior was examined by thermogravimetric analysis and differential scanning calorimetry. All the polymers showed a good thermal stability. At room temperature they appeared as semicrystalline materials, except the copolymers containing 20 and 30mol% of PI units: the main effect of copolymerization was a lowering in the amount of crystallinity and a decrease of melting temperature with respect to homopolymers. The crystalline phase of PPI and PPA was evidenced at high content of propylene isophthalate or propylene adipate units, respectively. Amorphous samples were obtained after melt quenching and an increment of T g as the content of PI units is increased was observed. This behavior was explained as due to the stiff phenylene groups in the polymeric chain. The Wood equation was found to describe well T g -composition data. Lastly, the presence of a rigid-amorphous phase was evidenced in the copolymers, differently from PPA homopolymer.