One of the factors affecting the electric charge acquired through friction between the polymers is their surface roughness. The dielectric barrier discharge (DBD) treatment is known to modify the surface characteristics of polymers. The aim of this study is to quantify the effect of atmospheric DBD exposure, in a well-defined configuration on the triboelectric behavior of polymers. Thus, Polytetrafluoroethylene (PTFE) plate samples characterized by different surface roughness were rubbed against bronze plate samples in a triboelectric test bench and then the electric potential at their surface was measured. The results were compared with those obtained for surfaces previously exposed to DBD treatment duration of which did not bring any change in their roughness. It was found that the roughness of the surface of the treated polymers hardly changed for rather short DBD exposure time (a few minutes). Significant changes were noticed for longer treatment duration (30 minutes and more). The samples that had undergone a longer treatment period modification acquired higher levels of electric charge by triboelectric effect.