Structures of AgAF(6) (A = Sb, Ta) have been determined by X-ray single crystal studies at ambient temperatures. AgSbF6 crystallizes in space group Ia (3) over bar with a = 979.85(4) pm, V = 9.4076(12) x 10(8) pm(3), z = 8, and AgTaF6 crystallizes in space group P4(2)/mcm with a = 499.49(4) pm, c = 960.51(8) pm, V = 2.3964(6) x 10(8) pm(3), z = 2. Only the crystal system and cell parameters were obtained for the isomorphic AgNbF6; primitive tetragonal, a = 497.80(10) pm, b = 960.40(10) pm, V = 2.3799(12) x 10(8) pm(3), z = 2. The results of the Raman spectroscopy of AgAF(6) support the obtained structures. The structures are discussed by comparing with that of AgPF6 and AgAsF6 which have recently been determined in a series of our study. (C) 2001 Elsevier Science B.V. All rights reserved.