The synthesis of a new anhydrous sodium manganese oxide α-Na0.66MnO2.13 obtained via a sol–gel process in organic medium is reported. The partial and limited removal of sodium ions from the layered host lattice (hexagonal symmetry; a =2.84Å, c =11.09Å) allows to get a high and stable specific capacity of 180mAhg−1 at C/20 in the cycling limits 4.3/2V with a mean working voltage of 3V without the emergence of a spinel phase. By introducing acetylene black in solution during the sol–gel reaction, a composite material containing 8wt.% AB has been obtained. The rate capability is shown to be significantly improved leading to an increase of the available specific capacity with for instance 200 and 90mAhg−1 at C/20 and C rate. This effect is ascribed to a better electronic contact between particles and/or the modification of the oxide surface which makes the intercalation process more homogeneous and more efficient.