ZrO2-mullite compound powders were synthesized with zircon and aluminum sulfate in molten sodium sulfate. Na2ZrSiO5 was prepared as intermediate with zircon and sodium carbonate at 900°C for 3h. Then the mixture of resultant Na2ZrSiO5 and aluminum sulfate was heated at different temperatures in molten sodium sulfate salt. The ZrO2-Al2O3-SiO2 compound powders were obtained after washing away the solvable salts. The results showed that the compound powders synthesized at 800°C were tetragonal ZrO2, SiO2 and Al2O3; the powders synthesized at 1000°C were monoclinal ZrO2 and mullite. The mullite in compound powders became to decompose when the reaction temperature increased over 1100°C.