Blends of corn starch with poly(ethylene-vinylalcohol) copolymer (SEVA-C) have been studied and reported as biodegradable. These materials are known to be sensitive to enzymatic action, evidencing a degradation of the starch phase in alpha-amylase assays. However, from the physical-chemical point of view the degradation of the blend is mainly associated with the leaching of glycerol, since other compounds are not released and no carbohydrates were found in the degradation solution. Based on these results, the present work attempts to determinate the respective diffusion coefficients. Four different experiments were performed, using samples with different thicknesses that were immersed in a simulated physiological solution. High performance liquid chromatography (HPLC) was used to separate the sugar derivatives and glycerol from the degradation solutions. The obtained data were fitted to an empirical model to allow the estimation of the diffusion coefficient for glycerol and glucose, based on the analytical solution for Fick's law of diffusion, and a good agreement was found (R(2) equals approximately 1). The glycerol leaches quickly out during the first few days of immersion, stabilizing thereafter, presenting greater diffusion coefficients for thicker samples. As the quantity of saccharides in the solution remains almost invariable along the experiments, this work also confirms that the degradation process is difficult without the action of enzymes.