The oxygen vacancy ordering process and displacive transitions have been characterised in the system CaTiO3-CaFeO2.5 as a function of composition and temperature at atmospheric pressure using X-ray diffraction, Mössbauer spectroscopy, infrared spectroscopy, transmission electron microscopy, electron energy loss spectroscopy, neutron diffraction and electrical conductivity methods. With increasing concentration of vacancies the following sequence is observed: isolated defects → short defect chains → infinite chains in layers. Similar experiments at high pressures and temperatures have been conducted to determine the nature of oxygen vacancies in the lower mantle phases (Mg,Fe)(Si,Al)O3-σ and Ca(Si,Fe)O3-σ perovskite.