Poly(vinyl alcohol) (PVA) layers of different thicknesses were intercalated into stereocomplex films composed of poly(L-lactide) and poly(D-lactide). The immersion of composite films into boiling water selectively extracted the water-soluble PVA components, resulting in porous stereocomplex films. The hydrolytic properties of the porous films under alkaline conditions were then quantitatively analyzed. It was observed that the hydrolytic rates decreased with increasing pore sizes.