New series dialkyltellurium(IV) diazides R2Te(N-3)(2) (R = CH3 (6), C2H5 (7), n-C3H7 (8), i-C3H7 (9), C-C6H11 (10)) and alkyl/aryltellurium([V) triazides R'Te(N-3)(3) (R' = CH3 (11), C2H5 (12), n-C3H7 (13), i-C3H7 (14), C6H5 (15), 2,4,6-(CH3)(3)C6H2 (16)) were synthesized by the straightforward substitution of fluorine atoms in the corresponding tellurium difluorides, or trifluorides respectively, with trimethylsilyl azide. In addition to standard characterization methods, the first crystal structures of covalent organotellurium(IV) triazides 12, 13, 14, and 16 have been determined. Ethyltellurium(IV) triazide , C2H5Te(N-3)(3) (12), crystallizes in the monoclinic space group F-2/n, a = 8.4530(2) Angstrom, b = 7,9094(2) Angstrom, c = 12.6288(3) Angstrom, beta = 91.876(1)degrees. n-Propyltellurium(IV) triazide, n-C3H7Te(N-3)(3) (13), crystallizes in the monoclinic space group P2(1)/n as well, a = 8.7999(2) Angstrom, b = 7,9674(2) Angstrom, c = 13.2334(3) Angstrom, beta = 94.626(1)degrees. Isopropyltellurium(IV) triazide, i-C3H7Te(N-3)(3) (14), crystallizes in the monoclinic space group C2/c, a = 20,058(2) Angstrom, b = 6.9620(3) Angstrom, c = 15.030(l) Angstrom, beta = 114.260(9)degrees. Mesityltellurium(IV) triazide, 2,4,6-(CH3)(3)C6H2Te(N-3)(3) (16), crystallizes monoclinic as well; the space group is P2(1)/c, a = 7,5503(6) Angstrom, b = 23.581 (1) Angstrom, c = 7.5094(6) Angstrom, beta = 91.295(9)degrees. The structures and vibrational frequencies of the methyl derivatives dimethyltellurium(IV) diazide (6) and methyltellurium(IV) triazide (11) have been calculated by density functional theory methods and were compared with the experimental metric parameters and vibrational data.