We have successfully prepared Li0.44+x Mn1−y Ti y O2 having the Na0.44MnO2-type framework structure by ion-exchange technique in molten LiNO3 and LiNO3–LiOH salts at 270 °C from the precursor Na0.44Mn1−y Ti y O2 synthesized at 800 °C using homogeneous and fine Mn–Ti hydroxides as starting materials. The needle-shaped particle length can be successfully reduced. The chemical composition and the crystal structure of Li0.44+x Mn1−y Ti y O2 were confirmed by using ICP–AES and XRD Rietveld analyses. The electrochemical measurements revealed that both the charge and discharge properties of the obtained Li0.44+x Mn1−y Ti y O2 samples were drastically improved. Especially, the obtained Li0.71Mn0.90Ti0.10O2 exhibited initial charge and discharge capacities of 176 and 212 mAh g−1, respectively, with an average discharge voltage of 3.56 V vs. Li/Li+. The resultant initial discharge energy density was achieved to be 755 Wh kg− 1. A further chemical lithiation treatment was performed using LiI for the Li0.63MnO2 and Li0.71Mn0.90Ti0.10O2 samples. The electrochemical measurements between 4.8 and 2.5 V for the lithiated Li0.83MnO2 and Li0.90Mn0.90Ti0.10O2 samples showed the improvement of the initial charge capacities. The rate capability test revealed Li0.90Mn0.90Ti0.10O2 retains 81% of its discharge capacity in going from 1C to 5C rate. The excellent high rate capability and good cycling performance of Li0.90Mn0.90Ti0.10O2 is particularly attractive for electric vehicle applications.