Zn1-xNixO (x = 0.001, 0.01, 0.02, 0.05 and 0.20) powders are prepared by sol-gel method. An extended x-ray absorption fine structure technique (EXAFS) for the Ni K-edge is employed to probe the local structures around Ni atoms doped in ZnO powders by fluorescence mode. The near edge EXAFS of the samples does not change in the range of Ni concentration from x = 0.001 to 0.05, which is consistent with the results of x-ray diffraction of the samples. The simulation results for the first shell EXAFS signals indicated that Ni atoms are substituted in Zn sites.