Triazidotriacetin (TAA) was synthesized via esterification and azidonation using propanetriol as raw material. The overall yield was 84.1%.The structures of intermediates and target compound were characterized by IR, NMR and elemental analysis. The factors affecting esterification and azidonation reactions were discussed. Results show that the optimum conditions of azidonation reaction are determined as: the dosage of NaN₃ is 1.10 times of theoretical value, i.e. n_exp:n_theo=1.10 (molar ratio), the dosage of water is 5%~25% of the total volume of acetone-water mixed solvent, and the reaction time is 10 h. The yield of TAA is 95.0% and its purity more than 96.8%.