Hexagonal ilmenite-type (Zn 1−x Ni x )TiO 3 (x=0, 0.85–1.0) ceramic powders were successfully synthesized by a sol–gel route with low temperature (800°C) sintering, which was modified by using the two-step heat treatment so as to obtain pure products. The thermal stability of the hexagonal (Zn,Ni)TiO 3 was enhanced with the increasing amount of nickel addition. FE-SEM observations demonstrated that the average crystallite sizes of (Zn 1−x Ni x )TiO 3 remarkably decreased from more than 200nm to less than 100nm with the increasing solubility x. The dielectric properties of (Zn 1−x Ni x )TiO 3 were measured at different frequencies and the results showed that there existed maximum values both for the dielectric constants and the loss tangents at x=0.85.