AbstractDiscrimination of elastically and inelastically scattered electrons in transmission electron microscopy (TEM) yields electron micrographs with enhanced and specific contrast. Highly resolved micrographs can be obtained in which the contrast reflects the local concentrations of specific elements. In the present work, Electron Spectroscopic Imaging (ESI) by means of a Zeiss EM 902 TEM is reported for polystyrene‐block‐poly(2‐vinylpyridine) diblock copolymers and for a series of differently crystallized polyethylene samples. Excellent contrast can be achieved without staining. The different techniques allow easy verification of the observed morph