Na4Ca3(AlO2)10 was synthesized at 1100~1250℃ with analytically pure reagents of CaCO3, Al2O3 and Na2CO3. The effects of leaching time, leaching temperature, liquid-to-solid ratio and concentrations of sodium carbonate and sodium hydroxide in solution on the leaching rate of Na4Ca3(AlO2)10 were examined. The results show that the purity of Na4Ca3(AlO2)10 roasted at 1200℃ for 30 min is over 90%. The alumina leaching rate can reach over 90% after its leaching at 40℃ for 10 min, when the concentrations of sodium carbonate and sodium hydroxide are 80 g/L and 18 g/L, respectively. The leaching rate can be more than 85% after its leaching at 60℃ for 15 min, when the concentration of sodium carbonate decreases to 30 g/L. Sodium hydroxide in the solution benefits the leaching process of Na4Ca3(AlO2)10. The leaching rate can be improved more than 10% when the concentration of sodium hydroxide is higher than 5 g/L. Na4Ca3(AlO2)10 has better leaching efficiency than 12CaO·Al2O3 and CaO·Al2O3.