We review the remarkable properties, including superconductivity, charge-density-wave ordering and metal–insulator transitions, of lead- and potassium-doped barium bismuthate. We will discuss some of the early theoretical studies of these systems. Our recent theoretical work, on the negative-U, extended-Hubbard model for these systems, will also be described. Both the large- and intermediate-U regimes of this model were examined, using mean-field and random-phase approximations, particularly with a view to fitting various experimental properties of these bismuthates. On the basis of our studies, we point out possibilities for exotic physics in these systems. We also emphasize the different consequences of electronic and phonon-mediated mechanisms for the negative U. We show that, for an electronic mechanism, the semiconducting phases of these bismuthates must be unique, with their transport properties dominated by charge±2eCooperon bound states. This can explain the observed difference between the optical and transport gaps. We propose other experimental tests for this novel mechanism of charge transport and comment on the effects of disorder.