Arrays of well-aligned single-crystal zinc oxide (ZnO) nanowires of uniform diameter and length have been synthesized on a (100) silicon substrate via a simple horizontal double-tube system using chemical vapor transport and condensation method. X-ray diffraction and transmission electron microscopy (TEM) characterizations showed that the as-grown nanowires had the single-crystal hexagonal wurtzite structure with detectable defects and a growth direction. Raman spectra revealed phonon confinement effect when compared with those of ZnO bulk powder, nanoribbons, and nanoparticles. Photoluminescence exhibited strong ultraviolet emission at 3.29 eV under 355 nm excitation and green emission at 2.21 eV under 514.5 nm excitation. No catalyst particles were found at the tip of the nanowires, suggesting that the growth mechanism followed a self-catalyzed and saturated vapor–liquid–solid (VLS) model. Self-alignment of nanowires was attributed to the local balance and steady state of vapor flow at the substrate. The growth technique would be of particular interest for direct integration in the current silicon-technology-based optoelectronic devices.