The reduction of La0.7Sr0.3Co0.8Fe0.2O3 (- delta) (LSCF7382) by heat-treatment in H-2 atmosphere or by electrochemical polarization has been followed by X-ray diffraction and Raman spectroscopy. The transition from perovskite ABO(3) to brownmillerite A(2)B(2)O(5) occurs at 250-300 degrees C in 10% H-2 atmosphere and is reversible. The Raman spectrum of brownmillerite shows two bands at 560 and 640 cm(-1) that we attribute to CoO4 tetrahedron stretching. Above 600 degrees C the sample starts to decompose irreversibly into Co, La2O3, SrO, and LaSrFeO4. This confirms that Co cations are more reducible than Fe ones. The Raman spectra obtained under cathodic polarization of the LSCF7382/CGO interface at 300 degrees C and PO2 = 10(-4) or 0.1 atm show the same bands as for the A(2)B(2)O(5) structure. This indicates that electrochemical reduction produces Co2+ in tetrahedral environment, even at low reducing overpotentials. Two reduction steps have been observed by linear sweep valtammetry and open circuit voltage relaxation. In both cases, Raman spectra indicate the presence of Co2+ in tetrahedral environment. The first reduction step is thus attributed to the reduction of B4+ within the perovskite phase and the second one to the reduction of Co3+ to Co2+ associated to the transition from perovskite to brownmillerite phase. Thermodynamic calculations from published literature support this idea. The association of n-type mobile species (Co2+) with oxygen vacancies is confirmed. (C) 2013 Elsevier B.V. All rights reserved.