ZnO nanowires doped with Mg have been successfully prepared on Au-coated Si (111) substrates using chemical vapor deposition method with a mixture of ZnO, Mg, and activated carbon powders as reactants at 850• C. The structural, compositional, morphological and optical properties of the samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and photoluminescence spectroscopy. The nanowires are single crystalline in nature and preferentially grow up along [0001] direction with the average diameter and length of about 60 nm and several hundred micrometers, respectively, thinner and longer than the results of literature using the similar method. Room temperature photoluminescence spectroscopy shows a blueshift from the bulk band gap emission, which can be attributed to Mg doping that were detected by energy dispersive X-ray analysis EDX in the nanowires. Finally, the possible growth mechanism of crystalline ZnO nanowires is discussed briefly.