Electrochemical reactivity is inherently local, governed by interfacial structure, transport phenomena, and surface chemistry at small length scales. Scanning electrochemical cell microscopy (SECCM) enables electrochemical measurements to be confined within a pipette-defined droplet, providing high spatial and temporal resolution for probing electrochemical processes at individual sites of the electrode surface. This approach facilitates direct correlation of electrochemical behaviour with structural and chemical information through correlative electrochemical multimicroscopy, enabling structure–property relationships to be established. Herein, SECCM has been applied to a broad range of functional materials, including nanostructured systems and compositionally complex, real-world materials such as multimetal alloys. Careful experimental design and data analysis allow local electrochemical activity to be linked to surface composition, morphology, and heterogeneity, revealing behaviour that is inaccessible using conventional ensemble-averaged techniques. These capabilities are particularly important for functional characterisation of materials where performance is governed by nanoscale variability. Beyond charge-transfer processes, electrochemistry in a pipette provides a unique platform for investigating electrochemically driven phase transitions in confined volumes. Of particular interest is the liquid–gas transition during reactions such as water reduction to hydrogen. Within the confined droplet geometry, gas mass transport and bubble dynamics are strongly influenced by the three-phase boundary between electrode, electrolyte, and air. SECCM enables controlled modulation of bubble nucleation, growth, and dissolution, offering new insights into the interplay between electrochemical kinetics, surface chemistry, and phase behaviour. These findings are relevant to applications ranging from electrolysis to metal processing and energy conversion technologies.