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Poly(butylene succinate) (PBSU) and poly(ε-caprolactone) (PCL) blends, both biodegradable chemosynthetic semicrystalline polyesters, were prepared with the ratio of PBSU/PCL ranging from 80/20 to 20/80 by co-dissolving the two polyesters in chloroform and casting the mixture. The miscibility and crystallization behaviour of PBSU/PCL blends were investigated by differential scanning calorimetry (DSC) and optical microscopy (OM). Experimental results indicated that PBSU was immiscible with PCL as evidenced by the composition independent glass transition temperature and the biphasic melt. However, during the crystallization from the melt at a given cooling rate, the crystallization peak temperature of PBSU in the blends decreased slightly with the increase of PCL, while that of PCL in the blends first increased and then decreased with the increase of PBSU. Moreover, both the crystallization peak temperature of PBSU and PCL shifted to the low temperature range with the increase of the cooling rate for a given blend composition. Double melting peaks or one main melting peak with a shoulder were found for both PBSU and PCL after the complete crystallization cooling from the melt, and were ascribed to the melting-recrystallization mechanism. It was found that the subsequent melting behaviour of PBSU/PCL blends was influenced apparently by the blend composition and the cooling rate used.