Graphene is a well-known emerging material with a wide range of applications. Despite its recent uses in polymer science, the immobilization of graphene on textile substrates is a major research thrust. Layer-by-layer (LBL) coating is a simple and cost-effective approach for stabilizing nanoparticles on different substrates to control properties, depending on the number of deposited layers. We assembled cationic graphene sheets using polyvinylphosphonic acid as an anionic thermal-resistant polymer on cotton via LBL coating. Fourier transform infrared spectra of the produced nanocomposite confirmed interfacial interactions among the graphene sheets, the polyvinylphosphonic acid and cotton in the coating layers; X-ray diffraction spectra revealed no changes in the cellulose bulk structure due to these interactions. Contact-angle measurements and thermogravimetric analyses showed that graphene and polyvinylphosphonic acid improved the thermal stability and hydrophobicity of cotton. Our results also suggest that graphene and polyvinylphosphonic are not only able to protect cotton against solar ultraviolet rays but also possess excellent near infrared reflectivity, electrical conductivity and electromagnetic shielding. These beneficial properties make nanocomposites promising structures for multifunctional applications.