In this study, we explore an approach to enhance the mechanical performance of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) by utilizing the self-reinforcing effect of β-phase-induced PHBV electrospun nanofiber mats. This involves electrospinning combined with low-temperature postspun vapor solvent interfiber welding. Scanning electron microscopy imaging confirmed fiber alignment, while XRD diffraction revealed the presence of both α and β crystalline phases under optimized electrospinning conditions. The resulting composite exhibited significant improvements in mechanical properties attributed to the formation of more perfectly structured α and β polymorphs and enhanced interfacial adhesion of electrospun nanofibers after vapor solvent treatment. This approach offers entirely recyclable and biodegradable materials, presenting the potential for a new family of sustainable bioplastics.