The effects of Ni substitution for Zn on microwave dielectric properties of (Zn1−xNix)3Nb2O8 (x=0.02–0.08) ceramics were investigated in this study. The XRD patterns of the sintered samples reveal single-phase formation with a monoclinic structure. The tremendous improvement of Q×f value can be achieved by a small level of Ni substitution (x=0.05). The τf value was found to decrease with a decreasing A-site bond valence. In addition, B2O3 and CuO were used as a sintering aid to lower the sintering temperature from 1180 to 900°C. Excellent microwave dielectric properties (ɛr∼20.7, Q×f∼98,000GHz and τf∼−85.2ppm/°C) and a chemical compatibility with Ag electrodes can be obtained for 4wt% B2O3–CuO doped (Zn0.95Ni0.05)3Nb2O8 ceramics sintered at 930°C for 2h. This constitutes a very promising material for LTCC applications.