The dependence of properties on the structure and morphology of semicrystalline polymers offers an effective way to tailor the properties of these materials through structure control. To this end

establishing the structure and property relationship is of great importance. For a right characterization of the crystal structure

several techniques can be used. Among these techniques

electron diffraction has its advantage for determining the crystal structure related to specific formation condition since it can combine with bright and dark fields observation of the sample. This feature article describes the application of electron diffraction in determining the crystal structure of semicrystalline polymers with elaborately selected examples. We focus on how the electron diffraction can be used to disclose the crystal structure

mutual orientation of different crystals

as well as the disorders included in the polymer crystals.