The method of crystallization of amorphous phase was applied to synthesize the different sodium titanate and the rules of crystalline structure transition to find the ways to synthesize different sodium titanates with single-phase and high crystallinity was studied. The crystallization of amorphous phase contains two parts, namely preparing amorphous phase and its crystallization. Preparation of amorphous sodium titanate is obtained by sintering TiO2 and Na2CO3 at 1200℃ for 1 h and then water-quenching. Crystallization of amorphous phase is carried out to synthesize sodium titanate by controlling the temperature, holding time and heating program. The results showed that single-phase Na2TiO3 and Na16Ti10O28 can be synthesize at 626℃ for 0 min and 811℃ for 120 min, respectively. The single-phase Na16Ti10O28, Na2TiO3, Na2Ti3O7 were synthesized at 897℃ for 0, 30 and 120 min, respectively. The average crystallinity at 626, 811 and 897℃ were 45.2%, 43.8% and 86.6%, respectively. In addition, it is found that gradual transition happens from amorphous phase to Na2TiO3 during the heating process, then transition happens from Na2TiO3 to Na4Ti5O12 at 626℃, further transits to Na16Ti10O28 at 811℃ and transits to Na2Ti3O7 at 897℃.