Zn0.84Mg0.16O and Zn0.12Mg0.88O nanowires with different morphology have been synthesized by a catalyst-free thermal evaporation method using Zn and Mg metals as the raw materials. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), and room-temperature photoluminescence (PL) measurements were used to determine the structure and optical properties of the obtained products. The obtained nanowires have diameters in a range of 30 nm-80 nm, crystallized well as hexagonal and cubic phase, with preferred orientation along the c-axis and a-axis for the two samples of Zn0.84Mg0.16O and Zn0.12Mg0.88O, respectively. Room-temperature PL at wavelengths of 384.4 and 495.8 nm has been observed for the sample of Zn0.84Mg0.16O. Upon annealing in Ar ambient, the emission peaks in PL spectra show a clearly blue shift.