X‐ray studies of unpoled and poled &ggr;‐form Nylon 11 films indicate that the polarization mechanism is not due to a field‐induced crystal transformation from the &ggr; to the &agr; form, suggesting the existence of a polar &ggr; form. The temperature dependence ofd31shows no decrease in polarization at the &agr;‐&ggr; transition temperature (∼95 °C), indicating that the hydrogen bonds in the poled film are not able to randomize. These results suggest the possibility that our understanding of the &ggr;‐form structure of Nylon 11 is incomplete.