Hexagonal Al-doped zinc oxide (ZnO) powders with a nominal composition of Zn1-xAlxO (0≤x≤0.028) were synthesized by the co-precipitation method. The contents of the Al element in the samples were measured by the inductively coupled plasma-optical emission spectroscopy (ICP-OES) technique. The structures of the Zn1-xAlxO (0≤x≤0.028) compounds calcined at 1000 and 1200℃ have been deter- mined using the Rietveld full-profile analysis method. Rietveld refinements of the diffraction data indi- cated that the addition of Al initially has a considerably positive effect on the decreasing of the lattice parameters a and c of Zn1-xAlxO, but the effect becomes very slight and even negative with the further increase of the Al content. The solid solubility limit of Al in ZnO (mole fraction y) is 2.2l%, resulting in Zn0.978Al0.22O. It seems that when the Al content is excessive, Al prefers to form a ZnAl2O4 compound with ZnO, but not to incorporate into the ZnO lattice to occupy the Zn2+ cites. Two phases, [ZnO] (or Al-doped ZnO) and [ZnAl2O4], are obviously segregated in Zn1-xAlxO while the value of x is larger than 0.024. The UV-Vis absorption spectra show that the Al-doped ZnO exhibits a red-shift in the absorption edge without reduced transmission compared with pure ZnO, which also confirms that Al ions enter the ZnO lattice and form a Zn1-xAlxO solid solution. Hexagonal Al-doped zinc oxide (ZnO) powders with a nominal composition of Zn1-xAlxO (0≤x≤0.028) were synthesized by the co-precipitation method. The contents of the Al element in the samples were measured by the inductively coupled plasma The structures of the Zn1-xAlxO (0≤x≤0.028) compounds calcined at 1000 and 1200 ℃ have been deter mined using the Rietveld full-profile analysis method. Rietveld refinements of the diffraction data indi- cated that the addition of Al initially has a substantial factor effect on the decreasing of the lattice parameters a and c of Zn1-xAlxO, but the effect becomes very slight and even negative with the further increase of the Al content. It seems that when the Al content is excessive, Al prefers to form a ZnAl2O4 compound with ZnO, but not to incorporate into the ZnO lattice to occupy the Zn2 + c The two-phase, [ZnO] (or Al-doped ZnO) and [ZnAl2O4], were distinct segregated in Zn1-xAlxO while the value of x is larger than 0.024. The UV-Vis absorption spectra show that the Al- doped ZnO exhibits a red-shift in the absorption edge without reduced transmission compared with pure ZnO, which also confirms that Al ions enter the ZnO lattice and form a Zn1-xAlxO solid solution.