The weakly coordinating pnicogen anion series, M(OTeF5)(6-) (M = As, Sb, Bi), has been synthesized as their tetraalkylammonium salts and have been structurally characterized by X-ray crystallography, F-19, As-75, Sb-121,Sb-123, Te-125, Bi-209 NMR spectroscopy, and Raman spectroscopy. The following crystal structures are reported : N(CH3)(4)As-+(OTeF5)(6-), trigonal system, space group , a = 10.109(2) Angstrom, c = 55.443(18) Angstrom, V = 4907 Angstrom(3), D-calc = 3.209 g cm(-3), Z = 6, R = 0.0644; N(CH3)(4)Sb-+(OTeF5)(6-), monoclinic system, space group : C2/c, a = 17.875(3) Angstrom, b = 10.448(2) Angstrom, c = 19.752(2) Angstrom, beta = 110.83(1)degrees, V = 3447.8 Angstrom(3), D-calc = 3.135 g cm(-3), Z = 4, R = 0.0710; N(CH2CH3)(4)Sb-+(OTeF5)(6-), monoclinic system,space group C2/c, a = 10.506(3) Angstrom, b = 18.370(6) Angstrom, c = 20.352(7) Angstrom, beta = 91.23(2)degrees, V = 3926.9 Angstrom(3), D-calc = 2.848 g cm(-3), Z = 4, R = 0.0548; N(CH3)(4)Bi-+(OTeF5)(6-), triclinic system, space group , a = 8.945(2) Angstrom, b = 9.217(2) Angstrom, c = 10.029(2) Angstrom, alpha = 100.03(3)degrees, beta = 99.95(3)degrees, gamma = 98.06(3)degrees, V = 789.5 Angstrom(3), D-calc = 3.606 g cm(-3), Z = 1, R = 0.0456. The central pnicogen atoms of the anions are bonded octahedrally to the six oxygen atoms and each of the six tellurium atoms is octahedrally bonded to an oxygen and five fluorines. Each anion structure can be described as composed of an octahedron of octahedra. Average M-O bond distances (corrected for libration) and M-O-Te bond angles are As-O = 1.807 Angstrom, Sb-O = 1.96/1.91 Angstrom, Bi-O = 2.065 Angstrom and As-O-Te = 140(2)degrees, Sb-O-Te = 150.9(8)/162.8(9)degrees, Bi-O-Te = 136.2(3)degrees. Low electric field gradients at the pnicogen nuclei result in spin-lattice relaxation times which are sufficiently long to allow for the observation of the NMR spectra of the four quadrupolar pnicogen nuclei and their couplings to Te-125. The anions are nonlabile on the NMR time scale in both SO2ClF and CH3CN solvents. Key frequencies,in the Raman spectra of the three anions have been assigned. The M(OTeF5)(6-) anions are likely to be weaker OTeF5- donors and less basic than,current examples of weakly coordinating anion derivatives of the OTeF5 group, i.e., B(OTeF5)(4-), Pd(OTeF5)(4)(2-), Nd(OTeF5)(6-) and Ti(OTeF5)(6)(2-).