Biomaterials play a critical role in implantable devices. They should present suitable structural/mechanical performance and biocompatibility, so that it is not recognized as foreign body by the immune system. Natural polymers such as chitosan (CHI) and alginate (ALG) fulfill the biocompatibility requirements, however present weak mechanical properties. The mechanical reinforcement effect can be enhanced with processing techniques that buildup nanostructure, such as layer-by-layer assembly (LbL). This was achieved with aqueous solutions of polyelectrolytes CHI and ALG. In this work, freestanding multilayered films containing CHI, ALG, and functionalized few-layer graphene (FLG) were produced through LbL assembly, envisaging the preparation of multifunctional films with mechanical and electrical performance. For that purpose, FLG obtained by different approaches was used, namely by production of graphene oxide (GO), stabilizer-assisted liquid phase exfoliation in aqueous solution of a pyrene derivative, and covalent functionalization of exfoliated graphite. Graphene nanoribbons (GNR) were produced by two covalent functionalization approaches, and their reinforcement effect was compared to that of FLG. Freestanding multilayered films were prepared by LbL, with compositions (CHI/ALG/CHI/ALG)100, (CHI/ALG/CHI/FLG)100, and (CHI/ALG/CHI/GNR)100. The films were characterized by thermogravimetric analysis, Raman spectroscopy, scanning electron microscopy, atomic force microscopy, water contact angle measurements, water uptake, degradation tests, uniaxial tensile tests, dynamical mechanical analysis, electrical conductivity measurements, and biological assays using L929 mouse fibroblasts. The high reinforcing effect of graphene, the changes induced on the electrical resistivity and the biocompatibility of the films were demonstrated.