To develop new series of tetrazole energetic materials， two new compounds， magnesium and calcium salts of 1，2-bis（tetrazol-5-yl）ethane （［Mg（BTE）（H₂O）₄］_n·nH₂O and ［Ca（BTE）（H₂O）₅］_n） were prepared. Their single crystals were obtained by solvent evaporation method. The structures were fully characterized by X-ray single crystal diffraction， elemental analysis and FT-IR method. The thermal decomposition behavior of two compounds were studied by DSC and TG-DTG methods Their non-isothermal kinetic parameters were calculated by the Kissinger method and Ozawa method. Results show that ［Mg（BTE）（H₂O）₄］_n·nH₂O belongs to monoclinic system，space group P2₁/c，cell parameters：a=9.0367（18） Å，b=9.1427（18） Å，c=7.4491（15） Å，β=103.51（3）°，Z=2. ［Ca（BTE）（H₂O）₅］_n belongs to orthorhombic system， space group Pnnm， cell parameters： a=11.205（2） Å，b=13.605（3） Å，c=7.1415（14） Å，Z=4.The temperatures of first exothermic peak for ［Mg（BTE）（H₂O）₄］_n·nH₂O and ［Ca（BTE）（H₂O）₅］_n are 387.7℃ and 415.8℃， respectively.