Nanostructural zinc oxide fibers have been fabricated by a simple vapor transport method of heating the mixture of zinc oxide, gallium oxide, and carbon powders in air. The zinc oxide nanofibers showed cauliflower-like, disordered, vertically and horizontally aligned morphologies in different temperature regions. The aligned nanofibers were composed of hexagonal zinc oxide with good crystallinity. Gallium was doped into zinc oxide with a concentration of 0.73 at. %. The growth process and the characteristics can be interpreted by a vapor-liquid-solid mechanism. The field emission of the vertically aligned zinc oxide fiber array showed a low field emission threshold, high current density, rapid surge, and high field enhancement factor. The threshold electric field is about 2.4 V/μm at a current density of 0.1 μA/cm−2. The field enhancement factor was 2991. The emission current density and the electric field followed the Fowler–Nordheim relationship.

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