[en] Salts of the OTeF₅^- anion were investigated by ir and Raman spectroscopy and by x-ray crystallography. Experimental results were compared with ab initio Hartree-Fock calculations on the OTeF₅ radical, Na⁺OTeF₅^-, and the singlet and triplet states of the free OTeF₅^-. The compound [(PS)H⁺][OTeF₅^-] was examined by single-crystal X-ray crystallography ((PS)H⁺ = protonated 1,8-bis(dimethylamino)naphthalene): bar P1, a = 8.241 (1) angstrom, b = 8.768 (2) angstrom, c = 12.591 (3) angstrom, α = 74.08 (2)degree, β = 78.00 (2)degree, γ = 80.23 (2)degree, Z = 2, T = -106 degree C. Unlike other salts of the OTeF₅^- anion, [(PS)H⁺][OTeF₅^-] did not exhibit any O/F disorder. Since the spectroscopic data for [(PS)H⁺][OTeF₅^-] closely matched those of [N(n-Bu)₄⁺][OTeF₅^-], it was concluded that this structure contains the best approximation of the structure of the free OTeF₅^- anion. The librationally corrected results are Te-O = 1.803 angstrom, Te-F_ax = 1.872 angstrom, Te-F_eq = 1.870 angstrom (average), and O-Te-F_eq = 95.2 degrees (average). A normal-coordinate analysis of OTeF₅^- was carried out by using this geometry and spectroscopic data for the ¹⁶O and ¹⁸O equivalents of [N(n-Bu)₄⁺][OteF₅^-]. 41 references, 5 figures, 8 tables