This work deals with the substantially high-temperature hydrogen sensors required by combustion and processing technologies. It reports the synthesis of undoped and Ni-doped TiO2 (with 0, 0.5, 1 and 2 mol.% of Ni) nanoparticles by a co-precipitation method and the obtained characteristics applicable for this purpose. The effect of nickel doping on the morphological variation, as well as on the phase transition from anatase to rutile, of TiO2 was investigated by scanning electron microscopy, X-ray diffraction and Raman spectroscopy. The resistive sensors prepared with these powders were tested toward H2 at 600 °C. The results indicate that 0.5% Ni-doped TiO2 with almost equal amounts of anatase and rutile shows the best H2 sensor response (ΔR/R0 = 72%), response rate and selectivity. The significant improvement of the sensing performance of 0.5% Ni-doped TiO2 is mainly attributed to the formation of the highest number of n-n junctions present between anatase and rutile, which influence the quantity of adsorbed oxygen (i.e., the active reaction site) on the surface and the conductivity of the material.