A novel nitrogen-rich energetic material 5H-[1, 2, 3]triazolo[4, 5-c][1, 2, 5]oxdiazole(2) was prepared via hydrolytic reaction using [1, 2, 5]oxadiazole [3, 4-e][1, 2, 3, 4]tetrazine 4, 6-di-N-oxide(FTDO) as raw material. Four new energetic derivatives, ammonium [1, 2, 3]triazolo [4, 5-c][1, 2, 5]oxdiazole(3), hydrazinium [1, 2, 3]triazolo[4, 5-c][1, 2, 5]oxdiazole(4), guanylureaium [1, 2, 3]triazolo[4, 5-c][1, 2, 5]oxdiazole(5) and triaminoguanidinium [1, 2, 3] triazolo[4, 5-c][1, 2, 5]oxdiazole(6) were designed and synthesized via reactions of compound 2 with ammonia gas, hydrazine hydrate, amidinothiourea hydrochloride and triaminogunidine nitrate, respectively. Their structures were characterized by IR, NMR and elemental analysis. The mechanism and conditions of hydrolytic reaction were analyzed. The optimal reaction conditions were determined as: the reaction time 5 h and reaction temperature 80 ℃ with a yield of 76.92%. The thermal properties of compounds, 2, 4, 5 and 6, were analyzed by DSC. Results show that their peak temperatures of initial decomposition reaction are 173.23, 144.82, 172.81, 164.94 ℃, respectively.