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Molecular transport through thin polymer films has become a subject with a variety of challenges and opportunities for chemists, physicists, and material scientists in recent years. The diffusion of probe molecules in and out of macromolecular environments plays a major role in the response of polymer-based sensor materials or the design of time-released drug delivery systems. Obtaining an improved understanding of the relevant dynamic phenomena, like transport of molecular probes, in boundary layers represents a crucial step to develop a clearer picture of the molecular transport processes taking place at interfaces modified with macromolecular assemblies. In this work, we present a new approach based on the derivation of the theoretical impedance transfer function to unambiguously describe the impedance response of gold electrodes modified with poly(methacryloyloxy)-ethyl-trimethyl-ammonium chloride (PMETAC) brushes. We demonstrate that this methodology not only enables the description of the experimental data but also provides insightful information about the dynamics of the diffusion of probe molecules inside the brush. More important, we show the capabilities of electrochemical impedance spectroscopy to gather information on a molecular transport process inside the brush under experimental conditions in which other electrochemical techniques are no longer applicable. As such, we consider that this experimental approach constitutes a new and powerful tool to estimate diffusion coefficients of probe molecules into interfacial macromolecular assemblies.