Spinel-structured (Zn1 - x(Li2/3Ti1/3)(x))(2)TiO4 (x = 0-1) microwave dielectric ceramics were manufactured via a conventional mixed-oxide method. The X-ray diffraction and Raman spectra revealed that a disordered face-centered cubic phase was found in the composition range of x < 0.5, and an ordered primitive cubic spinel solid solution was achieved as x was beyond 0.5. Such a disorder-order transition near x = 0.5 was accompanied by the variation of composition-induced cation occupancy. The Q x f value first kept increasing up to similar to 160 000 (GHz) in disordered ceramics, and then sharply decreased as an ordered structure appeared at x >= 0.5. An obvious decrease in tau(f) value was also accompanied by the appearance of an ordered structure. The minimum tau(f) value (similar to-20 ppm/degrees C) was obtained in the x = 0.75 sample with the highest structural order degree. These results demonstrated that microwave dielectric properties of current spinel ceramics could be successfully modified by adjusting their structural order degree, which could be appropriately adopted for the design of spinel-structured materials with favorable properties.