The microwave dielectric properties of Ca[(Li1/3Nb2/3)1−xMx]O3−δ (M = Sn, Ti, 0 ≤ x ≤ 0.5) ceramics were investigated. In general, the ceramics prepared were multiphase materials. However, single-phase specimens having orthorhombic perovskite structure similar to CaTiO3 could be obtained in the vicinity of Sn = 0.2 to 0.3, and Ti = 0.2. As Sn concentration increased, the dielectric constant (εr) decreased and the quality factor (Q) significantly increased within the limited Sn concentration. As Ti concentration increased, the dielectric constant (εr) increased, the quality factor (Q) decreased, and the temperature coefficient of resonant frequency (τf) changed from a negative to positive value. The temperature coefficient of resonant frequency of 0 ppm/°C was realized at Ti = 0.2. The Q · fo value and εr for this composition were found to be 26100 GHz and 38.6, respectively.