To comprehend the physical and chemical properties of porous materials and establish relationships between synthesis, structure and properties, a detailed understanding of the crystalline framework structures is vital. Recent developments of electron crystallography techniques, such as three-dimensional electron diffraction (3D ED) and aberration-corrected scanning transmission electron microscopy (STEM), have greatly facilitated structure elucidation. Three-dimensional electron diffraction (3D ED) is a technique that allows the acquirement of single-crystal diffraction data from submicrometersized crystals . Through 3D ED measurements, the requirement of synthesis optimization to grow large crystals, which is typically required for structure determination by single-crystal X-ray diffraction, can be circumvented, also significantly accelerating materials discovery. Automation in electron diffraction is now further accelerating materials discovery . Guest species have been located in the pores of nanoporous materials such as MOFs and germanium oxides 27 using 3D ED. STEM imaging has evolved into an essential technique for atomic-scale local structural investigations especially important for materials with structural disorders and low-dimensional materials. In combination with 3D ED, it represents a comprehensive toolbox for the characterization of both average and local structure, exemplified by the structure elucidation of bismuth subsalicylate and the discovery of the zeolitic nanotube .