Photoelectronic characteristics are investigated in well-aligned MgO-coated ZnO nanorods (MgO/ZnO nanocables) grown on Si substrates buffered with ZnO film at a low temperature by solution techniques. Transmission electron microscopy shows that a rough surface was observed for the MgO-coated ZnO nanorods due to deposition of MgO nanoparticles on the surface of the ZnO nanorods. However, after annealed at high temperatures, the surface of the MgO-coated ZnO nanorods was flattened to form Mg-doped ZnO nanorods. Photoluminescence spectra of Mg-doped ZnO nanorods displayed a blue shift of the near-band-edge emission with increasing annealing temperature indicative of an increase in the band gap of the MgZnO alloy due to diffusion of the Mg atoms into the ZnO nanorods. In contrast, no blue shift was detected for the samples annealed in H2/N2 (5%/95%) reduction atmosphere but a blue emission was detected at 800 degrees C, indicating that MgO diffusion process may produce a new luminescent center to emit the blue emission in H2/N2 reduction atmosphere.