Developing accurate electrophysiological recording platforms is crucial for investigating cellular electrical activities, understanding the mechanisms underlying cardiovascular disease, and advancing therapeutic strategies. While the successful recording of intracellular electrophysiological status has been achieved by 3D micro/nano devices, their preparation through demanding micro/nanofabrication and poorly controllable solvothermal synthesis is an impediment to widespread utilization. Easier‐to‐access recording electrodes are needed. To address this challenge, a simple and efficient supramolecular self‐assembly strategy that allows access to novel 3D electrodes is introduced. It relies on small organic molecules that can be self‐assembled efficiently into various 3D nanostructures, including lamellated nanosheets, thin nanobelts, and short rod‐like structures. Electrodes prepared through the present self‐assembly process are considerably simpler and more cost‐effective than conventional 3D micro/nanoelectrodes prepared through fabrication or solvothermal synthesis. It is demonstrated that the present electrodes allow for higher quality and prolonged intracellular recordings of action potentials as compared to similarly sized conventional planar electrodes. The noted improvements are attributed to the fact that 3D geometrical electrodes enhance the cell‐electrode interface, ensuring tight coupling and effective electroporation. This work showcases how supramolecular self‐assembly might emerge as a promising and powerful electrode preparation strategy that may facilitate low‐cost electrophysiological studies.