Fruits contain polyphenols, widespread antioxidants beneficial for human health. Their mass transfer was studied during the leaching of apple slices immersed in mannitol solutions with ranging concentrations (0, 0.2, 0.4, and 0.6 M). The solution of Fick’s law for unsteady mass transfer in planar configuration was used to calculate apparent diffusivity (De). Polyphenols were quantified by high-performance liquid chromatography for each immersion time. Leaching from raw apple tissues occurred only when cell integrity was lost, here at a certain level of difference in osmotic pressure. Different diffusivity values were found in the two apple varieties. Values of De either decreased from 0.2 to 0.1 × 10−9 and 0.2 × 10−9 m2 s−1 for Golden Delicious and Granny Smith, respectively, or were not determined when the mannitol concentration increased from 0 to 0.6 M. The osmotic strength of the solution strongly impacted the leaching rate of polyphenols from apple cells. The structure of the polyphenols also affected De, with low values for procyanidins.