Analytical methods of electrochemistry (EC) are relatively inexpensive, and widely used in science, industry, and medicine. Although EC is distinguished by its high sensitivity, it does not provide direct and detailed data about the bond connectivity or dynamics of the molecular system. Conversely, Magnetic Resonance (MR) gives comprehensive insights into the structure and dynamics of molecules but suffers from low sensitivity. The strengths and shortcomings of EC and NMR are thus complementary. The combination of these orthogonal techniques into EC-NMR creates a powerful tool that should be able to provide analytical data barely available for EC or NMR alone. This review presents recent developments in the field of EC-NMR – we describe experimental designs with electrodes made of metal wires, thin films, and nonmetallic materials, as well as performance improvements achieved by the implementation of micro-NMR, hyperpolarization, new pulse sequences, and 3D printing. We also review the application of EC-NMR in catalysis for sustainable energy conversion.