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The objectives of this study are to characterize the electronic state and local surrounding of 57Fe Mössbauer probe atoms within iron-doped layered perovskites La2Li0.5M0.5O4 (M = Co, Ni, Cu) containing transition metal in unusual formal oxidation states “+3”. Despite the fact that these oxides are characterized by similar crystal structure, the behaviour of 57Fe probe atoms in these lattices appears essentially different.