Detectors with cost-effective, polarization-sensitive, and integrative functionalities are required for next-generation ultraviolet (UV) detection systems. Low-dimensional semiconductor materials have potential for optical device applications, especially polarization detection, because of their excellent polarization characteristics. Therefore, ultralong ZnO microwires, ∼0.5 to 1 cm long, were prepared using the chemical vapor-phase epitaxy method, making it easy to build photoelectric devices. The emission polarization of the ZnO microwires excited by circularly polarized light was ∼0.60, indicating a high-anisotropy optical property. Their UV-polarization spectrum and photoelectric detection were determined. When the ZnO microwire was excited by linearly polarized UV light, the intensity of photoluminescence (PL) changed periodically with the polarization direction of the UV light. The PL polarization of the ZnO microwire for linear UV detection was ∼0.12. For a ZnO microwires photoelectric device, the photocurrent anisotropy ratio reached 1.28 when the polarization angle of the incident UV light changed. These results suggest that the obtained ultralong ZnO microwires have the potential for application in future UV-polarization detection systems.