Operando XANES and EXAFS spectra on the newly prepared Fe hexacyanocobaltate active material for positive electrodes in lithium batteries have been recorded at the XAFS beamline of Elettra using a suitable in situ cell. In this way, it was possible to follow in detail the main structural and electronic changes during the charge and discharge processes of the battery. The use of a chemometric approach for data analysis is also underlined.