Thin films of insulating polymers are sometimes analyzed by secondary ion mass spectrometry (SIMS) or by X-ray photoelectron spectroscopy (XPS) without the use of an electron gun. In this work, both SIMS and XPS have been used to study the chemical and structural modifications due to the charge effect during Cs+ sputtering of a thin film of polyvinyl chloride (PVC). The kinetic energy distribution study shows that at a small primary fluence similar to 10(15)Cs(+) ions/cm(2), the dielectric breakdown voltage of the PVC film is reached, i.e. the minimum voltage that causes a portion of an insulator to become electrically conductive. XPS study indicates that the conducting phase created in the PVC film after energetic Cs+ bombardment consists of graphitized carbon and metallic cesium clusters. After the dielectric breakdown of the film, the positive charge, previously accumulated on the surface, is neutralized through the conductive regions, which are created in the insulating film. During Cs+ sputtering of a PVC film, the chemical structure of the analyzed surface is completely modified and some ionic bonds such as Cs-C and Cs-Cl are also created. (C) 2013 Elsevier B.V. All rights reserved.