Most polymers are typical dielectric materials, but recent research in our group has shown that nanostructured block copolymer morphologies exhibit new and unexpected electroactive behavior. We present herein the fi rst study of converse piezoelectric properties in non-crystalline polymer systems, consisting of non-polar monomers, and evaluate its evolution with temperature to yield detailed information on electric fi eld‐ polymer interaction on a molecular level. The observed properties should hold generally and suggest that block copolymers may provide a valuable new route to piezoelectric materials. So far, mostly inorganic, perovskite structured ceramics, many of them titanate derivatives such as lead zirconate titanate (PZT), dominate the fi eld of commercial piezoelectric applications. Nanogenerators, fi eld-effect transistors, strain, and optoelectronic sensors are only few of many applications for this interesting class of materials. [ 1 , 2 ] Whilst the piezoelectric properties of many of these crystals and ceramics are well