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This paper reported the synthesis, crystal structure and electrical conductivity properties of Ni-doped ZnO powders (i.e. Zn_1-XNi_XObinary system, X=0, 0.0025, 0.005, 0.0075 and in the range 0.01≤X≤0.15). I-phase samples, which were indexed as single phase with a hexagonal (wurtzite) structure in the Zn_1-XNi_XObinary system, were determined by X-ray diffraction (XRD). The widest range of the I-phase was determined as 0≤X≤0.03 at 1200°C; above this range the mixed phase was observed. The impurity phase was determined as NiO when compared with standard XRD data, using the PDF program. We focused on single I-phase ZnO samples which were synthesized at 1200°C because of the widest range of solubility limit at this temperature. It was observed that the lattice parameters a and c of the I-phase decreased with Ni doping concentration. The morphology of the I-phase samples was analyzed with a scanning electron microscope. The electrical conductivity of the pure ZnO and single I-phase samples were studied by using the four-probe dc method at temperatures between 100 and 950°C in air atmosphere. The electrical conductivity values of pure ZnO and 3 mol% Ni-doped ZnO samples at 100°C were 2×10^-6 and 4.8×10^-6Ω^-1?cm^-1, and at 950°C they were 1.8 and 3.6Ω^-1?cm^-1, respectively. In other words, electrical conductivity increased with Ni doping concentration.