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High-quality Schottky devices based on ZnO microwires (MWs) by using a simple and effective method are reported. Cu-contained silver paste (SPC) was used as the contact electrodes of one end of ZnO MW-based metal-semiconductor-metal structures instead of the conventional method, in which customised silver paste was used as the contact electrodes of both ends of the structure. The experimental results reveal that SPC used in this study can increase the opportunity for obtaining the device with rectifying behaviour. The best-produced device exhibited a very high rectifying ratio of 105 at ±1±V. In addition, the rectifying I-V characteristics were greatly improved after annealing treatment because of the elimination of the bubbles in the conductive pastes. Moreover, the influence of contact area on the electrical properties was also investigated. It was shown that the contact area between ZnO MW and the electrode also played an important role in determining the rectifying performance.