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Birnessites containing Na, K or Li in the interlayer have been prepared by oxidation of Mn(II) cations with H2O2 in a basic medium with different alkaline cation/Mn molar ratios. The solids prepared have been characterised by elemental chemical analysis, powder X-ray diffraction, thermal analyses (differential thermal analysis and thermogravimetric analysis), FT-IR spectroscopy and surface texture assessment by adsorption of N2 at −196°C. Crystalline birnessites are obtained for A/Mn ratios (A = K, Li) larger than 3.4, but MnO(OH) has been also identificed when such a ratio is smaller than 3.4. Ion exchange is topotactic, but is not complete for exchanging Na, K, or Mg for pre-existing Li. The solids are stable up to 400°C, and formation of spinels and solids with tunnel structures is observed at this temperature. Li-containing birnessites are transformed to LiMn2O4 spinel at 400°C, and co-crystallization of bixbyte (Mn2O3) is observed at higher temperatures. Bixbyte and cryptomelane are formed at 500°C for the K-containing birnessites.