0.65CaTiO3–0.35LaAlO3 (CTLA) ceramic powder was synthesized by polymeric precursor method, using ethylenediaminetetraacetic acid (EDTA) as a complexing agent and glycol (EG) as an esterifying agent in complexing reaction. The process principle of polymer precursor method was analyzed and the effect of reaction conditions on polymer stability was studied. The results show that single CTLA with perovskite structure was synthesized when EDTA:metal-ion mole of ratio 1:1, EDTA:EG mole of ratio 1:2, and precursor solution pH was 6. Synthesis temperature reduced from 1200 °C of traditional solid-state reaction method to 700 °C, and the particle size of the powder is between 30 and 70 nm. Using the powder calcined at 950 °C as raw materials, the as-obtained CTLA ceramics were prepared sintered at 1325 °C for 3 h exhibited optimal microwave dielectric properties as εr = 41.8, Q × f = 34,151 GHz, and τf = − 5.8 × 10− 6/°C .