Large area Schottky diode with novel inverted vertical metal–semiconductor–metal type of structure (Pt/Ti/ZnO/Pt/SiO₂/Si) was demonstrated. The effects of crystallinity and native defects of ZnO films on the performance of Schottky diodes were investigated. Through oxygen plasma and post-annealing, the barrier height of Schottky diodes was dramatically enhanced, and the reverse leakage current was reduced by over six orders of magnitude. The obtained Schottky diodes with best performance of Schottky rectification exhibit the barrier height of 0.88 eV, and low reverse leakage current of 4.25 × 10⁻⁸ A cm⁻² under reverse bias voltage of −2 V. The novel structure was promising for the application of high performance opt-electrical devices.