Neutron total scattering data for α-Bi 2 O 3 and δ-Bi 2 O 3 , considering both the Bragg and diffuse components, have been analysed by the reverse Monte Carlo (RMC) method to extract experimental information concerning the short-range correlations between pairs of ions. These results complement the average structural information provided by conventional Rietveld refinement of the Bragg scattering alone. The radial and angular distribution functions in the stable ambient temperature α phase and superionic δ phase of Bi 2 O 3 are presented and compared with the corresponding data for the metastable β phase reported previously. These data provide an important insight into the nature of the anion disorder within the highly conducting δ phase and the relationship between the δ phase and its ordered α and β counterparts.