Modified Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] was prepared by melt reactive blending P(3HB-co-4HB) with chain extenders (ADR-4367). Thermal transitions, spherulitic and freeze-fracture morphology, mechanical and rheological properties of the chain extended bio-materials were investigated. The results show that glass transition temperatures and crystallization temperatures increase, crystallinity and diameters of spherulites decrease, there are amorphous parts dispersed among the crystalline phase, and the bio-materials transfer from brittleness to toughness and ductility. Steady shear viscosity of the modified P(3HB-co-4HB) increases by about one order of magnitude, melts of the modified P(3HB-co-4HB) behave more viscoelasticity by storage modulus and loss modulus correlated with oscillatory shear frequency. Addition of ADR-4367 with contents of 4~6 wt% in the blends is enough to branching and coupling the co-polymer chains and brings remarkable effect on improving mechanical properties, steady shear viscosity and viscoelasticity.