The ability to design the composition and microstructure of electronic ceramics for emerging technological applications requires sophisticated characterization techniques that can provide quantitative information about local structure and chemistry. Such structure quantification is particularly important to the fundamental understanding of properties in many electronic ceramics, where local heterogeneities associated with dopants or intrinsic lattice defects give rise to local inhomogeneities in charge, strain and polarization. Scanning transmission electron microscopy (STEM) provides an invaluable tool for probing such heterogeneities across several length scales, from picometer-scale lattice disorder to nanometer-scale grain boundary and interface segregation. This talk will review recent advances in STEM-based imaging and spectroscopy techniques, as well as advances in data analysis tools, which are driving the development of structure-processing relationships in electronic ceramics. Examples demonstrating the ability of STEM-based techniques to help interpret conductivity and polarization properties of modern electronic ceramics will be highlighted.