Seven compositions of LiMO2 ( M = L i w N i x C o y M n z ) ( w = 1 / 15 − 1 / 6 ; x =0−3/10; y =1/5−1/2; z =13/30−1/3; i.e. w + x + y + z = 1 ) solid solutions were synthesized using the sol–gel method with the following end members LiCoO2, Li2MnO3(Li[Li1/3Mn2/3]O2), and Li[Ni0.5Mn0.5]O2. The electrochemical behavior of the solid solutions was analyzed for the various compositions of metals in transition metal sites. All synthesized particles were semi-spherically shaped with a layered structure. When the content of lithium and cobalt was reduced (while the other metals were increased), the lattice parameters, a and c, decreased and were accompanied by a shift in the Raman spectrum. The cycling studies reveal that the compound, Li[Li1/12Ni1/4Co1/4Mn5/12]O2 was found to be optimal in voltage and from a stability point of view.