This study focuses on the dielectrical characterization of polycarbonate films coated with silica nanoparticle bilayers assembled through the Layer-by-Layer (LbL) technique. This is the first attempt of dielectric characterization performed on LbL-treated plastic substrates. To this aim, LbL coatings consisting of oppositely charged colloidal silica have been built on a polymeric substrate (polycarbonate). Then, dielectric features such as space charge accumulation, electrical voltage breakdown, and resistance to corona discharge (through laser ablation) have demonstrated that the colloidal silica nanoparticle assemblies can influence the nature of the trapped space charges and affect the resistance of polycarbonate to corona discharge, changing the distribution of the laser energy on impact. (C) 2013 Elsevier Inc. All rights reserved.