This paper focuses on the electrical characterization of polycarbonate substrates coated with silica/silica bi-layers assembled through the layer-by-layer (LbL) technique. More specifically, such dielectric features as the space charge accumulation are discussed and correlated with the number of silica/silica bilayers. Indeed, the nature of the trapped space charges seems to be affected by the LbL treatments, which polycarbonate has been subjected to.