(Al, W)-codoped ZnO powders with a constant molar ratio of Zn:Al (99:1) and various molar ratios of W:Al (0-0.02) were synthesized by a sol-gel process and characterized by X-ray diffraction, field emission scanning electron microscopy, and UV-vis and luminescent spectrophotometry. The experiments indicated that the powders illustrated increased c-orientation and a decreased average particle size with increasing W content. The W doping also resulted in the enhancement of transmittance in the UV-vis light range and the widening of the bandgap. Optimal efficiency appeared at molar ratio of W:Al = 0.01. Moreover, the W doping led to the formation of a new emission center and the enhancement of the emissions in range of visible light.