2O7 pyrochlores have fast-ion conduction properties that make them attractive candidates for applications in fuel cells. Rietveld powder-profile analysis of x-ray diffraction data has been used to determine structural parameters for Gd2(Ti1-ySny)2O7 solid solutions (y = 0.20, 0.40, 0.60, and 0.80) for correlation with composition-dependence of the specimens' electrical conductivity. In accord with Vegard's law, the lattice constants increase linearly with y as the larger Sn ion replaces Ti4+. The structures in the system remain remarkably ordered in view of the fact that it had been suggested that increasing the average radius of the ions that occupy the B4+ site relative to A3+ drives the system toward a disordered defect-fluorite state. A small but significant increase in mixing of the occupancy of the cation sites was found with increasing y to a maximum of [GdB] = 0.05. We could detect no significant disorder in the anion array. The activation energy and pre-exponential term for oxygen ion conduction were found to increase linearly and exponentially with y, respectively, such that at a given temperature, the ionic conductivity changes by less than an order of magnitude across the system. The behavior is in marked contrast to other systems where the substitution of a larger cation in the B site increases conductivity by up to three orders of magnitude as a consequence of substantial disorder that is introduced in both the cation and anion arrays.