Mg-doped ZnO radial spherical structures with nanorods grown on both sides of the spherical shell were successfully prepared via chemical vapor deposition (CVD) of Zn and Mg powders in the absence of a catalyst. The structures associated with different growth temperatures (700, 800, and 850℃) were monitored by scanning electron microscopy (SEM), and the result shows that the length of the nanorods increase progressively with the growth temperature increasing. X-ray diffraction (XRD) shows that the as-obtained samples can be indexed to high crystallinity with wurtzite structure. The growth of the nanostructures mainly depends on the formation of sphere-like Mg-doped Zn droplets before adding oxygen. Photoluminescence (PL) spectra that show a 39 meV blue shift indicates that the band gap becomes large, because Mg substitutes Zn in the lattice.