Ga2O3-core/ZnO-shell coaxial nanocables were fabricated via a two-step process. While Ga2O3 core nanowires were synthesized by thermal heating of GaN powders, ZnO shell layers were deposited on the core nanowires by using the atomic layer deposition method. The samples were characterized by using scanning electron microscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and photoluminescence spectroscopy (PL). XRD, lattice-resolved TEM, and selected area electron diffraction revealed that the coated shell layers comprised a hexagonal ZnO phase. EDX analyses were in good agreement with what can be expected for the ZnO-coated Ga 2O3 nanowires. The shape of PL spectrum has been changed by the coating process, suggesting a contribution from ZnO shell layers.