The electric-double-layer (EDL) formed at liquid/solid interfaces provides a broad and interdisciplinary attraction in terms of electrochemistry, photochemistry, catalysts, energy storage, and electronics because of the large interfacial capacitance coupling and its ability for high-density charge accumulation. Much effort has recently been devoted to the fundamental understanding and practical applications of such highly charged EDL interfaces. However, the intrinsic nature of the EDL charging, whether it is electrostatics or electrochemistry, and how to distinguish them are far from clear. Here, by combining electrical transport measurements with electrochemical impedance spectroscopy (EIS), we studied the charging mechanisms of highly charged EDL interfaces between an ionic liquid and oxide semiconductor, ZnO. The direct measure for mobile carriers from the Hall effect agreed well with that from the capacitance-voltage integration at 1 Hz, implying that the pseudocapacitance does not contribute to carrier transport at EDL interfaces. The temperature-frequency mapping of EIS was further demonstrated as a "phase diagram" to distinguish the electrostatic or electrochemical nature of such highly charged EDL interfaces with densities of up to 8 X 10(14) cm(-2), providing a guideline for electric-field-induced electronic phenomena and a simple method for distinguishing electrostatic and electrochemical charging in EDLTs not only based on a specific oxide semiconductor, ZnO, but also commonly applicable to all types of EDL interfaces with extremely high-density carrier accumulation.