As a typical broad bandgap semiconductor, ZnO has received considerable attention for developing optoelectronic devices in ultraviolet wavelengths, but suffers from a lack of high-quality single-crystalline p-type ZnO. Herein, we report the realization of a homojunction ultraviolet photodetector, which involves a p-type Sb-doped ZnO microwire (ZnO:Sb MW) and n-type ZnO layer. The p-type conductivity of the as-synthesized ZnO:Sb MWs was evidenced using an individual wire field-effect transistor. Due to its good rectifying ability and excellent photovoltaic effect, the constructed p-ZnO:Sb MW/n-ZnO homojunction is able to work as an ultraviolet photodetector in self-biased and reversely biased manners. By appropriately engineering the band alignment of the p-ZnO:Sb/n-ZnO homojunction via a MgO interface modification layer, the optimized photodetector exhibits performance-enhanced ultraviolet detection capabilities, such as the light on/off ratio reaching up to 1.6 × 108, responsivity of over 267 mA W-1 and specific detectivity of approximately 1.2 × 1014 Jones upon 365 nm light illumination at 0 V. The detector also produces faster response with rise/recovery times of 102 μs/3.6 ms. This study not only employed a novel method to synthesize genuine p-type ZnO with excellent stability and reproducibility, but also opened up substantial opportunities for developing high-performance ZnO homojunction optoelectronic devices.