In this paper, (Sr0.9Ca0.1)1/2La1/2Al1/2Ti1/2O3-x wt.% CeO2 (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) ceramics were synthesized via solid state reaction. The effects of Ce4+ doping on microstructure and microwave dielectric properties were studied. All samples crystallized as perovskite single-phase. Ce4+ substitution for La3+ occurred at the A site for 0 < x ≤ 0.4, and for Ti4+ at the B site for 0.4 ≤ x ≤ 0.5. Oxygen vacancy concentration was linked to substitution sites, decreasing for x ≤ 0.3 and increasing for x ≥ 0.4, as shown by XPS analysis. The quality factor was influenced by oxygen vacancies, grain size, and packing fraction. Bonding valence and oxygen octahedral distortion affected the temperature coefficient of resonant frequency. At x = 0.4 and sintered at 1570 °C, the ceramics showed excellent properties: εr = 38.83, Q×f = 54058 GHz, τf = 2.137 ppm/°C, making it a promising low-loss dielectric ceramic for microwave communication applications.