The combination of liquid nuclear magnetic resonance spectroscopy (NMR) and electrochemistry (EC) is a new technique with promising prospect which provides novel, exciting, and crucial insights into the processes near or on the electrode surface at a molecular or atomic level. The development of in situ EC-NMR spectroscopy with flow or static electrolysis was summarized, the structures of the electrolysis cell and the characteristics of the NMR spectra were analyzed, and the feature of the in situ EC-NMR spectroscopy in practice was described in detail. The electrolysis electrode located at radio-frequency detection area of the NMR spectrometer reduced homogeneity of the magnetic field. Furthermore, the electrolysis current results in broadened spectral lines and loss of resolution. The working electrode consisting of a thin metal film and the electrolysis current parallel to the static magnetic field can overcome such shortcomings. Besides, several high-resolution methods in inhomogeneous fields were discussed and compared, such as intramolecular multiple quantum coherences, nutation echos, intermolecular nuclear Overhauser effects, and intermolecular multiple quantum coherences.