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Persistent spectral holes in a thin film of poly(vinyl butyral) doped with a substituted Zn‐tetrabenzoporphin show irreversible broadening effects when high electric field strengths (some hundred kV/cm) are applied. A small field (a few kV/cm) with opposite sign, however, cancels the broadening almost completely and restores the original hole width. Therefore, the broadening is not due to field‐induced spectral diffusion, but to permanent electric fields generated in the sample. Our interpretation in terms of electret theory shows that the source of these fields is charges near the surface of the sample, which are injected from the electrodes.