ZnO was prepared using room temperature bipolar electrochemical process in deionized water. Electron microscopy, powder X‐ray diffraction, and micro‐Raman spectroscopy showed crystallization of the material into the wurtzite hexagonal structure of ZnO, self‐organized in micro‐sized flower‐like shapes that are formed out of individual nanorods preferentially grown along the <0thinmathspace0thinmathspace0thinmathspace1> direction. The intrinsic electronic properties were evaluated by potentiodynamic electrochemical impedance spectroscopy using Mott–Schottky analysis of semiconductor/liquid junctions. Because the flat band and carrier density are frequency‐dependent, we used an approximation based on fractional order capacitance fitting, and subsequently three different ways to calculate the frequency‐independent effective capacitance of the system. The capacitance computed using the four parameters of single‐dispersion Randle's model, i.e., pseudocapacitance, dispersion coefficient, and series and parallel resistances, is more recommended for the characterization of the electrochemical system.