Poly[R-3-hydroxybutyrate-co-(R-3-hydroxyvalerate)] (PHBVs) copolymers are promising biopolymers, which could substitute petroleum-based plastics for various applications. PHB and PHBV pellets were processed on a customized 3D printer via Fused Granular Manufacturing (FGM) approach modified with a Mahor screw extruder. To anticipate the behaviour of PHBVs when transformed using conventional thermo-mechanical shaping processes, thermal and mechanical analyses were carried out in order to better understand the effect of annealing temperature on their crystallization behaviour and mechanical properties of PHB polymer and PHBV copolymer. The objectives of the present work were to propose an experimental strategy to study the melting and crystallization events, crystalline structure changes, and mechanical performances of both PHB homopolymer and PHBV copolymer according to identical thermal annealing treatments. A monitoring of 3D printed PHB and PHBV structures was achieved by coupling Differential Scanning Calorimetry (DSC) and tensile tests.