A comprehensive description of the electrochemical mechanisms of the Prussian blue analogue (PBA) K1.67Mn0.65Fe0.35[Fe(CN)6]0.92•0.45H2O is obtained by combining several complementary ex situ and operando physicochemical characterisation techniques. This particular PBA, which shows very good electrochemical performance as a cathode material in potassium-ion batteries (PIBs), undergoes three successive redox reactions during the (de-)potassiation that are hereby identified by ex situ 57 Fe Mössbauer spectroscopy and operando Mn and Fe K-edge X-ray absorption spectroscopy. These reactions come along with notable modifications of the crystal structure, which are followed in real time by operando X-ray diffraction. The correlation of these results, interpreted with the support of chemometric methods, also reveals the limitations of this PBA, probably related to the deactivation of the Mn undergoing extensive reversible Jahn-Teller distortion during cycling as well as possible dissolution in the electrolyte. These results underline that optimisation of the chemical composition of PBAs is a crucial step towards the preparation of reliable and stable PBA-based cathodes for PIBs.< Leer menos