We prepared (1−x)CaTiO₃–xLaAlO₃ (0 ≤ x ≤ 1) microwave dielectric ceramics using a conventional two-step solid-state reaction method, and investigated microwave dielectric properties of the ceramics in terms of A/B-site ionic-parameters. Ionic-parameters such as ionic polarizability, A-site bond valence, and ionic rattling were linked to the microwave dielectric properties. As the LaAlO₃ content x in the (1−x)CaTiO₃–xLaAlO₃ ceramics increased from 0.3 to 0.7, the dielectric constant gradually decreased, which was attributed to the decrease of polarizability deviation and suppression of the cation rattling. The temperature coefficient of the resonant frequency decreased as the content of LaAlO₃ increased because of the increase of A-site cation bond valence. The quality factor value (Q × f) increased as LaAlO₃ content increased because of the enhancement of the order degree of B-site cation. A significant deterioration of the temperature coefficient of the resonant frequency and Q × f value was observed at the composition x = 0.5. These decreases were attributed to a phase transition from orthorhombic crystal (for x ≤ 0.5) to rhombohedral crystal (for x > 0.5).