Titanium containing γ -MnO 2 octahedral molecular sieves having hollow sphere structures are successfully prepared for the fi rst time using a one-step synthesis method. Titanium cations are used as structure-directing agents in the synthesis process. The assembly of the hollow spheres is carried out at the beginning of the process. Various techniques including XRD, N 2 adsorption, SEM, EDX, RAMAN, TEM, XPS, and TGA are employed for the materials characterization. Ti is incorporated into the MnO 2 framework in isolated sites, and TiO 2 phases (anatase and rutile) are not observed. When introduced in medium-sized lithium-air batteries, the materials give very high specifi c capacity (up to 2.3 A h g − 1 ). These materials are also catalytically tested in the oxidation of toluene with molecular oxygen at atmospheric pressure, showing signifi cant oxidative catalytic activities in this diffi cult chemical reaction.