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Blends of poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) and poly(butylene succinate) (PBSU), both biodegradable semicrystalline polyesters, were prepared with the ratio of PHBV/PBSU ranging from 80/20 to 20/80 by co-dissolving the two polyesters in chloroform and casting the mixture. Differential scanning calorimetry (DSC) and optical microscopy (OM) were used to study the miscibility and crystallization behaviour of PHBV/PBSU blends. Experimental results indicate that PHBV is immiscible with PBSU as shown by the almost unchanged glass transition temperature and the biphasic melt. Crystallization of PHBV/PBSU blends was studied by DSC using two-step crystallization and analyzed by the Avrami equation. The crystallization rate of PHBV decreases with the increase of PBSU in the blends while the crystallization mechanism does not change. In the case of the isothermal crystallization of PBSU, the crystallization mechanism does not change. The crystallization rate of PBSU in the blends is lower than that of neat PBSU; however, the change in the crystallization rate of PBSU was not so big in the blends. The different content of the PHBV in the blends does not make a significant difference in the crystallization rate of PBSU.