The self-organization of thin polymer films into functional patterns is important both scientifically and technologically. Electric fields have been exploited as an efficient and powerful means to induce the destabilization and self-organization of soft materials. Previous attention, however, has mainly focused on externally applied electric fields. It is shown herein that the internal electric field is strong enough to guide the self-organization of thin polymer films as well. Patterns of electrostatic charges with micrometer resolution are first introduced on a dielectric substrate. A thin polymer film is then spin-coated onto the topographically flat substrate. Upon thermal annealing, the thin polymer film destabilizes due to a lateral gradient of electrostatic stress and flows away from the electroneutral regime to the charged area, resembling the patterns of charges on the substrate. Theoretical and numerical modeling based on the electrohydrodynamic instability shows excellent agreement with experimental observations both qualitatively and quantitatively. It is also demonstrated that the interplay between charge-driven instability with spinodal dewetting and Rayleigh instabilities can generate finer and hierarchical polymeric patterns that are completely different from the charge patterns preintroduced on the substrate. This study provides direct evidence that the internal electric field caused by charges on the substrate is strong enough to destabilize thin polymeric films and generate patterns. This study also demonstrates new strategies for bottom-up fabrication of structured functional materials.