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By means of in vitro experiments, performed with a three compartment diffusion cell, we show how the presence of surfactants, often present in the formulation of dentifrices and mouthrinses, may affect the availability of calcium and its permeation rate through the proteic layer covering dental enamel (acquired pellicle). Mucin was the protein used to simulate the pellicle. Experiments were performed at different surfactant concentrations (i.s. below and above CMC) and also in the presence of fluoride ions that are capable of enhancing enamel remineralization. The mechanisms involved, mainly related to the interaction of surfactant monomers with the model protein, are discussed in this paper.