Nanostructured electrochemical interfaces (electrodes) are found in diverse applications ranging from electrocatalysis and energy storage to biomedical and environmental sensing. These functional materials, which possess compositional and structural heterogeneity over a wide range of length scales, are usually characterized by classical macroscopic or "bulk" electrochemical techniques that are not well-suited to analyzing the nonuniform fluxes that govern the electrochemical response at complex interfaces. In this Perspective, we highlight new directions to studying fundamental electrochemical and electrocatalytic phenomena, whereby nanoscale-resolved information on activity is related to electrode structure and properties colocated and at a commensurate scale by using complementary high-resolution microscopy techniques. This correlative electrochemical multimicroscopy strategy aims to unambiguously resolve structure and activity by identifying and characterizing the structural features that constitute an active surface, ultimately facilitating the rational design of functional electromaterials. The discussion encompasses high-resolution correlative structure-activity investigations at well-defined surfaces such as metal single crystals and layered materials, extended structurally/compositionally heterogeneous surfaces such as polycrystalline metals, and ensemble-type electrodes exemplified by nanoparticles on an electrode support surface. This Perspective provides a roadmap for next-generation studies in electrochemistry and electrocatalysis, advocating that complex electrode surfaces and interfaces be broken down and studied as a set of simpler "single entities" (e.g., steps, terraces, defects, crystal facets, grain boundaries, single particles), from which the resulting nanoscale understanding of reactivity can be used to create rational models, underpinned by theory and surface physics, that are self-consistent across broader length scales and time scales.