Several La0.05Sr0.95CoO3-y (LSCO-95) powders were synthesized by means of a chelated complex-based precursor approach, which involved pyrolysis of chelating precursors and subsequent calcination of the resulting oxides. This paper focuses on the coordination effects of the precursors on the formation of the crystalline phases of the LSCO-95 oxide, showing that when the precursor is composed of EDTA-metal complexes, the perovskite-type oxide LSCO-95, an electronic-ionic mixed conducting ceramic material, can be achieved. In contrast, those LSCO-95 powders obtained initially from the pyrolysis of the precursors containing other coordination ligands possess only the undesirable hexagonal structure, (C) 2000 Elsevier Science Ltd.