The phase structure and biodegradability were investigated for amorphous blends of chemosynthetic fully amorphous atactic poly(R,S-3-hydroxybutyrate) (a-PHB) with atactic poly(methyl methacrylate) (PMMA) and atactic poly(R,S-lactide) (a-PLA). The differential scanning calorimetry thermal analysis indicated that a-PHB/PMMA blends were partially miscible while a-PHB/a-PLA blends were miscible in the studied composition range. The biodegradations of the blends were carried out in phosphate buffer solution in the presence of bacterial poly(R-3-hydroxybutyrate) extracellular depolymerases purified from Alcaligenes faecalis T1 and P. stutzeri. Although a-PHB in the pure state was not degraded by these depolymerase, it was degraded by blending with PMMA and a-PLA. The results demonstrated that the enzymatic degradation of a-PHB can be induced by amorphous polymers such as PMMA and a-PLA. Also, the biodegradation rate of a-PHB in the blends decreased drastically when the degradation temperature is too much away from the polymer glass transition temperatures. On the basis of these results, a temperature window of the enzymatic degradation was first proposed for the blend and the essence of induced degradation was discussed.