(1-x)ZnAl2O4–xTiO2 (x = 0.21) ceramics were synthesized at 1500 °C using the solid-state reaction after the starting powders were calcined at 1050–1250 °C. The effects of calcining temperature on the microstructures, phase compositions, and microwave dielectric properties of the ceramics had been investigated. In the calcined (1-x)ZnAl2O4–xTiO2 (x = 0.21) powders, the amount of the secondary phase Zn2Ti3O8 decreases gradually with increasing calcining temperature and it disappears at more than 1150 °C. The εr and Q·f values increase slowly with increasing calcining temperature and then decrease after reaching the maximum value at 1150 °C, whereas the τf values are nearly independent of the calcining temperature and approach zero. When the calcining temperature reaches 1150 °C, the optimal microwave dielectric properties of the (1-x)ZnAl2O4–xTiO2 (x = 0.21) ceramics can be exhibited with a εr of 11.6, a Q·f of 74,000 GHz (at about 6.5 GHz), and a τf of -0.4 ppm/°C.