Novel poly(vinyl alcohol) (PVA)/poly(vinyl butyral–vinyl alcohol) (P(VB-VA)) films with improved hydrophobicity were prepared from poly(vinyl acetate) (PVAc)/poly(vinyl butyral) (PVB) blend films with various mass ratios by saponification in a heterogeneous medium. The successful conversion of PVAc to PVA and PVAc/PVB to PVA/P(VB-VA) films was confirmed by Fourier transform infrared spectrometry, X-ray diffraction, and proton nuclear magnetic resonance analysis. This study also shows that the degree of saponification (DS) depends on the saponification time. The maximum DS of 99.99% was obtained at 96 h of saponification for all films, and the presence of PVB did not affect the DS at saponification times of 48–96 h. The effects of the PVAc/PVB blend ratio before and after saponification were determined by contact angle measurement, and the hydrophobicity was found to increase in both cases with increasing PVB content. Additionally, all the films exhibited improved mechanical properties after saponification, and the treated films possessed an unusual porous and uneven surface, in contrast with the untreated films. The prepared films with improved hydrophobicity can be used for various applications, such as biomaterials, filters, and medical devices.