A family of Sr-doped perovskite compounds Ln(1-x)Sr(x)CoO(3-delta) (Ln = La3+, Pr3+ and Nd3+; x > 0.60), were prepared by sol-gel chemistry and reaction at 1100 degrees C under 1 atm of oxygen. This structural family has been shown to be present only for rare earth ions larger than Sm3+ and an upper limit of Sr2+ solubility in these phases was found to exist between x = 0.90 and 0.95. X-ray diffraction shows oxygen-deficient, simple cubic (Pm-3m) perovskite crystal structures. The combination of electron and powder neutron diffraction reveals that oxygen vacancy ordering occurs, leading to a tetragonal (P4/mmm) superstructure and a doubling of the basic perovskite unit along the crystallographic c-axis. No additional Ln(3+)/Sr2+ cation ordering was observed. (c) 2005 Elsevier Ltd. All rights reserved.