Display omitted ► Novel hybrids based on PVDF and different contents of Cu nanoparticles have been prepared. ► A complete structural and morphological characterization of the nanocomposites has been performed. ► Interactions between PVDF matrix and Cu nanoparticles is deduced from FTIR. ► Attenuation of the electromagnetic radiation increases spectacularly with the Cu content. Novel hybrids based on PVDF and varied concentration of Cu nanoparticles have been prepared in order to analyze their electromagnetic interference shielding response and, consequently, their capability to be a good alternative to replace metals for that application. Very promising results have been found in this area. Moreover, a complete structural and morphological characterization, as well as a previous evaluation of their mechanical behavior, has also been performed.