Polycrystalline samples of the pyrochlore series (Ag1-xMxSbO3+x[(n-1)/2])-Sb-n (M = Na, K, and Tl) have been structurally analyzed through total scattering techniques. The upper limits of x obtained were 0.05 for Na, 0.16 for K, and 0.17 for Tl. The Ag+ cation occupies a site with inversion symmetry on a 3-fold axis. When the smaller Na+ cation substitutes for Ag+, it is displaced by about 0.6 angstrom perpendicular to the 3-fold axis to achieve some shorter Na-O bond distances. When the larger Tl+ cation substitutes for Ag+, it is displaced by about 1.14 angstrom along the 3-fold axis and achieves an environment typical of a lone pair cation. Some of the Tl3+ from the precursor remains unreduced, leading to a formula of Ag0.772(1)Tl0.13(2)+Tl0.036(1)3+SbO3.036(1). The position of the K+ dopant was effectively modeled assuming that K+ occupied the same site as Ag+. The expansion of the lattice caused by substitution of the larger K+ and Tl+ cations results in longer Ag-O bond lengths, which would reduce the overlap of the Ag 4d and O 2p orbitals that compose the valence band maximum. Substitution of the smaller Na+ results in a decrease in the Ag O bond distance, thus increasing the overlap of the Ag 4d and O 2p orbitals. This will have a direct influence on the band composition and observed properties of this material of interest.