The distribution of an anionic surfactant, sodium dodecyl sulfate (SDS), in waterborne acrylic films was investigated, focusing on the effects of particle composition and size, and pH of the latex. The observed surfactant distributions could be classified in two categories: homogeneous and heterogeneous, the latter showing SDS aggregates. The shape of the profiles was related to the stability of the latex during drying, at short interparticular distances. The stability of the latex was determined by the presence or not of fixed charges at the surface of the particles. The latices with particles carrying neutralized acrylic acid at high pH (COO-) led to homogeneous distributions, whereas the latices with acrylic acid at low pH (COOH) or without acrylic acid led to heterogeneous distributions. Our interpretation is that the stable latices present a narrow network of paths between particles at high polymer volume fraction, limiting the mobility of the surfactant, whereas in the less stable latices wider routes between flocs allow enough mobility for large aggregate formation. Thermal treatments of the dry films confirmed the strong confinement of the surfactant in the dense film structure obtained at high pH and the more open structure, allowing easier surfactant transport and oxygen penetration, observed at low pH. In order to account for the shapes of the profiles more quantitatively, a model was developed based on the diffusion of the surfactant and its transport by the drying front. It was found that the apparent diffusion coefficient of SDS micelles had to be lowered to a great extent (D = 10(-13)-10(-14) m(2)/s) during drying in order to explain aggregate formation. It should be even lower (D = 10(-15) m(2)/s) to interpret homogeneous surfactant profiles. These results are consistent with our hypothesis of the key importance of the surfactant mobility during drying.