The effect of dopant on microwave dielectric properties of (1-x)MgTiO3-xCaTiO3 ceramics, known to be used as microwave dielectric resonators for global positioning system and personal communication system, has been analyzed in terms of variations in defect concentrations and microstructural features with its addition. The addition of dopants was revealed to result in a significant change in the microstructure as well as defect concentration of the ceramics. For instance, the quality factor is proportional to sintered density of the ceramics by inversely proportional to grain size as well as vacancy concentration. Accordingly, it is believed that the dopant effect on the microwave dielectric properties should be separately analyzed with either microstructural change or the change in vacancy concentration.