Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) has gained significant attention because of its biodegradability and sustainability. However, its expanded application in some fields is limited by the brittleness and low melt viscoelasticity. In this work, poly(vinyl acetate) (PVAc) was introduced into PHBH/poly(propylene carbonate) (PPC) blends via melt compounding with the aim of obtaining a good balance of properties. Dynamic mechanical analysis results suggested that PPC and PHBH were immiscible. PVAc was miscible with both a PHBH matrix and PPC phase, while it showed better miscibility with PHBH than with PPC. Therefore, PVAc was selectively localized in a PHBH matrix, reducing interfacial tension and refining dispersed phase morphology. The crystallization rate of PHBH slowed down, and the degree of crystallinity decreased with the introduction of PPC and PVAc. Moreover, the PVAc phase significantly improved the melt viscoelasticity of ternary blends. The most interesting result was that the remarkable enhancement of toughness for PHBH/PPC blends was obtained by adding PVAc without sacrificing the strength markedly. Compared with the PHBH/PPC blend, the elongation at the break and yield strength of the PHBH/PPC/10PVAc blend increased by 1145% and 7.9%, respectively. The combination of high melt viscoelasticity, toughness and strength is important for the promotion of the practical application of biological PHBH.