Several 3,6-disubstituted 1,2,4,5-tetrazines were synthesized by nucleophilic substitution using 3,6-bis-(3,5-dimethyl-pyrazol-1-yl)-1,2,4,5-tetrazine and 3,6-dichloro-1,2,4,5-tetrazine as electrophiles. All new compounds were characterized by 1 H NMR, 13 C NMR and vibrational spectroscopy, mass spectrometry and elemental analysis (C,H,N). For analysis of the thermostability, differential scanning calorimetry (DSC) was used. Especially, the symmetrically bis-3,5-diamino-1,2,4-triazolyl-substituted derivative shows a very high thermal stability up to 370 • C. Therefore its energetic properties were determined and compared with thoses of hexanitrostilbene (HNS). The crystal structures of 3,6-bishydrazino-1,2,4,5-tetrazine, 3,6-dichloro-1,2,4,5-tetrazine and 3-amino-6-(3,5-diamino-1,2,4-triazol-1-yl)-1,2,4,5-tetrazine dihydrate have been determined by low-temperature X-ray diffraction.