Biopolymers are preferred ingredients for the manufacture of materials because they are based on abundantly available and renewable raw materials that have benign environmental problems associated with their production, fabrication, use, and disposal; however, the wide use of biopolymers in engineering applications has not been achieved, mainly because of the inferior quality of many biopolymer-based products. To overcome this limitation, studies have been initiated on blends of biopolymers and biodegradable synthetic polymers. We used the contact angle of probe liquids to measure the surface energy of polystyrene, the biodegradable polyesters polycaprolactone, poly(hydroxybutyrate-co-hydroxyvalerate) polylactic acid, polybutylene adipate terephthalate, and adipic poly(hydroxy ester ether), and normal starch. The surface energies were used to estimate the starch/polymer interfacial energy and work of adhesion. The calculated starch/polyester work of adhesion showed mixed correlation with published starch/polyester mechanical properties, indicating that factors other than interfacial properties might be dominant in determining the mechanical properties of some starch/polyester blends.