Summary The new field of applications for triboelectric materials is based on the combination of high physical durability and charge properties of ZnO semi‐conductor thin films, which have been explored in this work. ZnO films are successfully deposited by the RF magnetron sputtering method in the wurtzite phase. A post‐heat‐treatment process of the as‐deposited films is carried out in an oxygen atmosphere at 973 K. According to the X‐ray diffraction patterns, scanning electron microscope (SEM), and atomic force microscopy (AFM) images, the average particle size of the ZnO films increases gradually with the heat‐treatment process. The semilogarithmic current‐voltage and frequency‐dependent capacitance measurements of thin films under various bias voltages are done to understand the charge transfer resistance, conductivity and capacitance properties which directly affect the figure of merit (FOMm) of the triboelectric layer material performance. The charge density and triboelectric charge density values in present study for heat‐treated thin films are 11 and 121 mC/m2, respectively. These findings might be used as a good candidate for further triboelectric device energy research areas in the near future.