A correlation between oxygen site distributions and ionic conductivity has been established in the recently discovered family of oxide-ion conductors Ba3M2O8.5±δ (M = Nb, V, Mo, W). We rationalize this observation on the basis of structural insights gained from the first single-crystal neutron diffraction data collected for a member of this family, Ba3NbWO8.5, and theoretical considerations of bonding and O site energies.