The phase relations and microwave dielectric properties of (1−x)ZnNb2O6–xTiO2 were investigated using x-ray powder diffraction and a network analyzer. Four phase regions were studied with increasing TiO2 mol% (x): columbite solid solution, ixiolite (ZnTiNb2O8) solid solution, mixture of ixiolite and rutile solid solutions, and rutile solid solution. It was suggested that the microwave properties depend on crystal structure rather than chemical composition. In the columbite solid solution region, an order–disorder transition was found with an increasing amount of TiO2, and the quality factor decreased sharply. ZnTiNb2O8 (x = 0.5), has a fully disordered structure and possesses a quality factor of 42,500, relative dielectric constant (εr) of 34.3, and temperature coefficient of resonant frequency (τf) of −52 ppm/°C. In the mixture region of ixiolite and rutile structure, τf was modified to around 0 ppm/°C.