AbstractThe influence of high electrostatic fields on Raman scattering has been studied. For fields approaching 108V m−1in polymers a contribution to the Raman intensity due to the non‐linearity of the Raman polarizability could be demonstrated. These results are in agreement with theoretical considerations. The band position does not change within the achieved resolution of 0.1 cm−1for fields up to 1.7 × 108V m−1, as also expected from theoretical estimates. With pulsed fields of duration<1 μs, field strengths exceeding the static breakdown strength could be applied. In this case, however, a very complex pre‐breakdown behaviour was observed, influencing the Raman scattering in a manner not yet