Synthesis of various X-birnessites was performed using the ion exchange properties of the sodium birnessite Na0.32MnO2,yH(2)O. Their structural and electrochemical characteristics are investigated and discussed in comparison with previous data obtained for some compounds and in relation with mechanism invoked for Li electrochemical insertion into sol-gel and chemical birnessites. Two main groups of materials are obtained with a monoclinic or hexagonal structure depending on the kind of inserted cation.