The avalanche photodiode is a highly sensitive photon detector with wide applications in optical communication and single photon detection. ZnO is a promising wide band gap material to realize a UV avalanche photodiode (APD). However, the lack of p-type doping, the strong self-compensation effect, and the scarcity of data on the ionization coefficients restrain the development and application of ZnO APD. Furthermore, ZnO APD has been seldom reported before. In this work, we employed a p-Si/i-ZnO/n-AZO structure to successfully realize electron avalanche multiplication. Based on this structure, we investigated the band structure, field profile, Current-Voltage (I-V) characteristics, and avalanche gain. To examine the influence of the width of the i-ZnO layer on the performance, we changed the i-ZnO layer thickness to 250, 500, and 750 nm. The measured breakdown voltages agree well with the corresponding threshold electric field strengths that we calculated. The agreement between the experimental data and calculated results supports our analysis. Finally, we provide data on the impact ionization coefficients of electrons for ZnO along the (001) direction, which is of great significance in designing high-performance low excess noise ZnO APD. Our work lays a foundation to realize a high-performance ZnO-based avalanche device.