Electrochemical analysis enables us to characterize the performance of a wealth of chemical systems. However, the complexity and scale of many chemical systems, including nanoscopic objects and highly localized interfacial regions, calls for more sophisticated approaches that provide key details to understand and manipulate them. Coupled spectroscopic methods shed light on intricate details of molecular structure and reactivity. Using the combined power of photons and electrons enables a new understanding of molecular-scale phenomena that underpin selectivity and energy efficiency in electrochemically driven processes relevant to synthesis, energy conversion and chemical sensing. The adaptation of stimulated Raman spectroscopy (SRS), scanning electrochemical microscopy (SECM) with co-localized Raman microscopy imaging, confocal Raman microscopy and vibrational sum-frequency generation (VSFG) spectroscopy in the study of electrified interfaces and nanostructured electrode materials are highlighted. These techniques help seed new directions in our thinking of electrochemical interfaces and their transformations.