Since the enzymatic degradation of microbial poly[(R)-3-hydroxybutyrate-co-3-hydroxyvalerate] (P(3HB-co- 3HV)) initially occurs by a surface erosion process, a degradation behavior could be controlled by the change of surface property. In order to control the rate of enzymatic degradation, plasma gas discharge and blending techniques were used to modify the surface of microbial P(3HB-co-3HV). The surface hydrophobic property of P(3HB-co-3HV) film was introduced by CF3H plasma exposure. Also, the addition of small amount of polystyrene as a non-degradable polymer with lower surface energy to P(3HB-co-3HV) has been studied. The enzymatic degradation was carried out at 37 ºC in 0.1 M potassium phosphate buffer (pH 7.4) in the presence of an extracellular PHB depolymerase purified from Alcaligenes facalis T1. Both results showed the significant retardation of enzymatic erosion due to the hydrophobicity and the enzyme inactivity of the fluorinated- and PS-enriched surface layers.