An energetic plasticizer 4, 4, 4-trinitrobutyric acid 2-azido-1-azidomethyl-ethyl ester(DPTB) was synthesized via esterification reaction from 4, 4, 4-trinitrobutyric acid(TNB)and 1, 3-diazido-propan-2-ol(DAG), in which, TNB was prepared via nitration-hydrolysis and addition reaction using 4, 6-dihydropyrimidine as raw material, and DAG was prepared via azidation by 1, 3-dichloro-propan-2-ol as raw material. The structure of DPTB was characterized by IR, NMR and elemental analyses. In synthesis, traditional esterification method was replaced by dicyclohexylcarbodiimide(DCC)/dimethylaminopyridinium p-toluenesulfonate(DPTS) catalytic esterification method. The effects of material ratio, reaction temperature, reaction time and solvent dosage on the esterification reaction were investigated. The thermal decomposition properties of DPTB were studied by thermogravimetry(TG) and differential scanning calorimetry(DSC). Results shw that replacing traditional esterification method with DCC/DPTS catalytic esterification method makes the yield of DPTB promote from 17.9% to 44.9%.There are two exothermic peaks at 215 ℃ and 230 ℃ on DSC curve of DPTB. Its TG curve can be divided into two stages: first-stage is from147 ℃ to 220 ℃ accompanied with 76.68% mass loss; second-sstage is from 220 ℃ to 351 ℃ accompanied with 15.23% mass loss and the total mass loss from start to the end of decomposition reaction is 91.19%.