Sb-doped p-type ZnO microwires with zigzag rough surfaces were synthesized by two zone chemical vapor deposition. The zigzag morphology characteristics analyzed by high resolution scanning electron microscopy and transmission electron microscopy show the existence of surface defects caused by Sb doping. The incorporation of Sb into a ZnO lattice induces lattice imperfection, which is the origin of the zigzag rough surface. Photoluminescence and electrical properties of the obtained Sb-doped ZnO microwires were determined. The crossed structure microwire-based p–n homojunction device was fabricated by applying as-synthesized Sb-doped p-type ZnO microwires and undoped n-type ZnO microwires. The doped microwires demonstrate reproducible p-type conduction and enhanced rectifying behavior with increasing Sb doping concentration. The results demonstrated that the optimizable optical and electrical characteristics, controlled by increasing the doping concentration, are reflected in the surface morphology changes which would be helpful for characterizing the doping effects in micro/nanoscale materials.