Magnesium (Mg) with a concentration range of 1 to 3 at% was successfully doped in zinc oxide (ZnO) and prepared via a hydrothermal process in powder form. X-ray diffraction patterns revealed a polycrystalline nature of the prepared powders. Images taken by a scanning electron microscope showed that the synthesized powders had clear solid hexagonal rod structures. Furthermore, the solid hexagonal structures were hollow because of the Mg ions introduced into the ZnO. The photoluminescence emission of the undoped and Mg-doped ZnO showed an enhancement of the ultraviolet emission with the Mg concentrations. Furthermore, the Gaussian fitting reveals that the UV band emission is consist of two emissions. The first peak was at 3.36 eV for the undoped ZnO that shifts to 3.4 eV, 3.43 eV for the 1 at% Mg and 2 at% Mg concentration, respectively. Thereafter the UV peak position reduced to 3.39 eV for the 3 at% Mg ions concentration. The results were studied, and the correlation of the results was attributed to the doping process.