The electrical conductivity of CaTi1-xFexO3-delta (x = 0-0.5) was measured as a function of temperature and oxygen partial pressure. At 1000 degreesC, the highest conductivity was observed at x = 0.2. The crystal structure of the materials with x = 0, 0.2, 0.25, and 0.3 was studied by x-ray powder diffraction and refined by the full-profile analysis method. The results were used to elucidate the mechanisms of the high-temperature (greater than or equal to 1000 degreesC) formation, ordering, and transport of oxygen vacancies in CaTiO3 upon substitution of Fe3+ for Ti4+. The composition dependences of ionic conductivity calculated for CaTi1-xFexO3-delta agree well with experiment.