The development of sustainable materials by employing natural and nontoxic resources has been attracting much attention over the previous years. In this work, we discuss for the first time the chemical combination between resorcinol diglycidyl ether (RDGE), an aromatic biobased thermosetting monomer, and polyhydroxybutyrate (PHB), a bioderived and biodegradable thermoplastic polyester. By this combination, we aimed to associate the high thermal stability of RDGE with a toughening effect by the aliphatic chains of PHB. The investigations on the mechanism of the cross-linking reaction and on the structural connectivity between the two components were realized by Fourier transform infrared (FTIR) and NMR spectroscopies. We found that the epoxide polymerization catalyzed by tertiary amines triggers the formation of crotonyl species by polyhydroxybutyrate cleavage. Two-dimensional NMR experiments show that polyhydroxybutyrate fragments covalently bind as side chains to the rigid aromatic network of the epoxide frame. The cross-linking between the two systems entails the formation of new ester and ether bonds. The obtained structures show a network homogeneity confirmed by a single T-g, from 85 to 47 degrees C, as a function of the formulation, and tan delta values from 87 to 53 degrees C. The combination of the two comonomers showed a positive effect. The PHB increased the toughness of RDGE-based thermosets, improving the material elasticity by increasing the chain length between the cross-links. An important result of this study is the high thermal stability of RDGE/PHB bioresins, with the T(5% )varying between 330 and 310 degrees C as a function of the PHB ratio.