Layered LiMn1−x M x O2 (M=Zn or Fe) (0≤ x ≤0.3) samples are synthesized from the corresponding sodium analogues by an ion-exchange method using LiBr in n-hexanol at 160°C. The samples are subjected to physicochemical and electrochemical characterization. X-ray diffraction data indicate the formation of layered structures for the LiMn1−x Zn x O2 samples up to x =0.3 and for LiMn1−x Fe x O2 samples up to x =0.2. Among these, LiMn0.95Zn0.05O2 and LiMn0.95Fe0.05O2 provide the highest capacity values of 180 and 193mAhg−1, respectively. Both Zn- and Fe-substituted samples display good capacity retention up to 30 charge–discharge cycles. Electrochemical impedance spectroscopy and galvanostatic intermittent titration data corroborate the results obtained from cyclic volatmmetry and charge–discharge cycling.