A new family of bioabsorbable materials suitable for biomedical applications was designed and prepared by means of blending of some available polyesters to develop new biodegradable materials tailored for different requirements. Multiphase polymer blends containing poly(d, l-lactide) (PLA), poly(epsilon-caprolactone) (PCL), poly(d, l-lactide-co-poly(ethylene glycol) (PELA), poly(epsilon-caprolactone)-co-poly(ethylene glycol) (PECL), and poly(beta-hydroxybutyrate) (PHB), PLA/PCL, PELA/PECL, PHB/PLA, PHB/PELA, PHB/PCL, and PHB/PECL blends were respectively investigated. It was found that PLA/PCL, PHB, and PHB/PLA and PHB/PCL blends were seemingly immiscible, with their morphology and hydrolytic behavior were determined by the composition of the blends. On the other hand, the miscibility of PELA/PECL, PHB/PELA, and PHB/PECL blends was improved by using PELA and/or PECL block copolymers that contained poly(ethylene glycol) (PEG) as compatibilizer. The blends showed to a certain extent miscibility, fine phase morphology, and fast hydrolysis.