With the aim of mimicking the plant cell wall, a layer by layer approach was used to build a thin film consisting of successive adsorption of pectin and extensin. Elaboration of the thin film was monitored by surface plasmon resonance, quartz crystal microbalance, and ellipsometry. All data indicate that formation of the film was successful and that growth occurred according to a nonuniform growth. It is likely that diffusion of the polymers occurred within the multilayer structure and that the final structure is not constituted by layered individual pectin and extensin films. Polymer rearrangements were also supported by the atomic force microscopy images that show a smoother surface after extensin adsorption than after pectin deposition.