Poly(vinyl alcohol) (PVA) cast gels with high degrees of polymerization and hydrolysis were prepared at room temperature. After sufficient exchange of the outer solvent by fresh pure water, the gel was re-dissolved in pure water at a high temperature. Using this solution, the cast gel was prepared again. This re-dissolution process was repeated again, and a third cast gel was prepared. During each swelling process after each cast-drying process, the amount of elution from the gel was measured and the molecular weight distributions of PVA in the gel as well as in the outer solvent were quantitatively evaluated. The molecular weight distribution of the eluted PVA was found to depend on that of the PVA in the gel; the average molecular weight gradually increased as the re-dissolution process was repeated, while the polydispersity indices of both the PVA from the gel and the eluted PVA decreased.