The structural refinements of CaTi1-xFexO 3-δ (x = 0 - 0.4) were performed by means of the X-ray data full-profile analysis method on the basis of the orthorhombic perovskite structure (space group Pbnm). The lattice parameters, atomic coordinates, occupancies and equivalent isotropic temperature factors were refined. The characteristic Debye temperature value was determined for the composition x = 0.25 by analysis of the temperature dependence of X-ray reflections intensity. Using the structural refinement results, the model of oxygen vacancy formation, ordering and transport under acceptor doping was proposed. The dependence of the ionic conductivity on the iron concentration in CaTi1-xFe xO3-δ calculated in the frame of proposed model describes well the experimental data.