Ecocomposites made up of polystyrene and starch were produced by co-grinding. The mechanism by which the composite is formed was identified by following the particle size and morphology. The size reduction of the matrix particles is favoured by the presence of starch which adheres on polystyrene surface, playing the role of agglomeration inhibitor between matrix particles. Thus, the filler is well dispersed in the matrix, permitting a good homogeneity of the composite properties. The hydrophilic behaviour of starch is reduced by co-grinding, resulting of a decrease of the acid and non dispersive components of the surface energies. Consequently the interactions between the initially hydrophobic matrix and hydrophilic filler are enhanced without using a compatibilizer. Thus, the water-resistance of the co-ground composite materials is better compared to blends since blends pellets introduced in water are rapidly disintegrated while an adapted co-grinding time permits to avoid this problem. It was seen that the diffusion coefficient of water in the composite pellets decreases with an increase of the co-grinding time for the lower filler rates, while it is the opposite for high filler rates. Moreover, the diffusion coefficient increases with the filler ratio. (C) 2010 Elsevier B.V. All rights reserved.