Uniform and continuous Al2O3 thin films were prepared by the chemical liquid deposition (CLD) method. The breakdown field strength of the amorphous CLD-Al2O3 film is 1.74 MV/cm, making it could be used as a candidate dielectric film for electronic devices. It was further proposed to use the CLD-Al2O3 film as an electron blocking layer in a triboelectric nanogenerator (TENG) for output performances enhancement. Output voltages and currents of about 200 V and 9 µA were obtained, respectively, which were 2.6 times and 3 times, respectively, higher than TENG device without an Al2O3. A colloidal condensation-based procedure controlled by adjusting the pH value of the solution was proposed to be the mechanism of CLD, which was confirmed by the Tyndall effect observed in the growth liquid. The results indicated that the CLD could serve as a low-cost, room temperature, nontoxic and facile new method for the growth of functional thin films for semiconductor device applications.