Most of the studies conducted to date with regard to surface science for biodegradable polymers focused on the investigation of the effect of surface modification of the polymers on the degradation behavior or on the effect of external materials such as biosurfactants on the surface properties of biomaterials. Although some reviews have discussed a broad range of polymer surface characterization, none of them have dealt with biodegradation of polymers in terms of surface reactivity. This paper reviews the role of the determination of surface reactivity as a means to contribute to the understanding of biodegradation kinetics and controlled drug release mechanism for some important biodegradable polymers such as poly(α-hydroxy acid)s, exemplified by poly(glycolic acid) and poly(lactic acid).