The aim of the present work was to assemble extracellular matrix components into polyelectrolyte multilayers using the layer-by-layer deposition method. The films are constructed with type-I collagen and hyaluronic acid. The construction exhibits the general features observed during polyelectrolyte multilayer buildup: alternate positive and negative values of the zeta potential of the film during its construction and regular increase of the film thickness with the number, n, of deposition step. This increase is shown to be linear with n. As expected for a linearly growing film, the confocal microscopy shows that when the film is brought in contact with a collagen solution, collagen does not diffuse into the film but interacts only with its outer layer. However, the films are not constituted of homogeneously distributed polyanion/polycation complexes as it is usually observed, but they are formed of fibers as imaged by AFM. The typical width of these fibers increases with the number of deposition steps. Finally, it is found that chondrosarcoma cells spread well and synthesize extracellular matrix components only on the collagen ending films, whereas no cellular matrix was found for HA ending ones. Such architectures may be further functionalized by inclusion of active drugs, peptides, proteins..., and could be used as tunable biomaterial interfaces.