LiCo1−x Fe x O2 compounds (0≤x≤ 1) with ordered rock salt structure of α-NaFeO2 type were prepared by ion exchange reaction in a molten eutectic mixture from the corresponding Na compounds. The Li compounds are investigated by galvanostatic and potentiostatic cycling experiments. The new form, ion-exchanged LiCoO2 (IE-LiCoO2), is compared in its electrochemical behaviour with the known high temperature HT-LiCoO2. A different behaviour at cycling up to 4.8V versus Li/Li+ is evidenced. Galvanostatic and potentiostatic cycling experiments were also carried out on the iron-containing compounds. Charge voltage increases and electrochemical capacity decreases with increasing iron content and reaches a low value for LiFeO2 with an iron content of x=0.6. Reasons that may account for this behaviour are discussed.