In this study, the 3D printability of a series of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)/poly(lactic acid) (PLA) blends were investigated using fused filament fabrication (FFF). The studied blends suffered from poor 3D printability due to differences in compatibility and low thermal resistance. These shortcomings were addressed by incorporating a functionalized styrene-acrylate copolymer with oxirane moieties as a chain extender (CE). To enhance mechanical properties, the synergistic effect of 3D printing parameters such as printing temperature and speed, layer thickness and bed temperature were explored. Rheological analysis showed improvement in the 3D printability of PHBV:PLA:CE blend by allowing a higher printing temperature (220 °C) and sufficient printing speed (45 mm s −1). The surface morphology of fractured tensile specimens showed good bonding between layers when a bed temperature of 60 °C was used and a layer thickness of 0.25 mm was designed. The optimized printing samples shown higher storage modulus and strength, resulting in stiffer and stronger parts. The crystallinity, morphology and performance of the 3D printed products were correlated to share key methods to improve the 3D printability of PHBV:PLA based blends which may be implemented in other biopolymer blends, and further highlight how process parameters enhance the mechanical performance of 3D printed products. Conventional sources of energy such as fossil fuels are becoming less sustainable and reliable due to our limited natural resources 1. The development of greener materials with at least similar mechanical properties to conventional feedstock is of importance for their successful implementation in manufacturing sectors such as additive manufacturing (AM) 2. Fused filament fabrication (FFF) is an AM technology in which thermoplastic materials are melted and deposited layer by layer onto a free surface platform 3. FFF allows freedom of design, which facilitates prototyping and customization of products in a timely and cost-effective manner. Due to the nature of FFF processing, material properties are highly anisotropic and research on materials, as well as printing parameters such as layer width, thickness, raster angle and air gap between layers, is vital for the optimization of fabricated products 3-6. Consequently, previous researchers have determined that layer orientation of 0° raster angle in the axial load direction results in higher tensile properties, while products with build orientation angles of ± 45° have improved impact strength and less warping 7-9. Polyhydroxyalkanoates (PHAs) are gaining immense attention in the field of biopolymers due to their inherent nature such as biodegradability, biocompatibility and promise for use in a range of applications, especially in the biomedical industry 10,11. In addition, PHAs are reducing the high dependency on petroleum-based materials. Among PHAs, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is currently one of the most widely produced and commercialized bioplas...