Lithium-rich composite cathodes have been extensively investigated for lithium-ion batteries. Nanoarchitecture hydroxide precursor for these cathodes with two levels of particle agglomeration (1–2 μm and 10 μm) is produced using a co-precipitation method. Transmission electron microscopy and X-ray diffraction confirm that the precursor is a composite comprising transition metal hydroxides and Mn3O4. Cathode materials synthesized based on the precursor are “layered (Rm)-layered (C2/m)-spinel (Fdm)” composite phase. The electrochemical performance of lithium cells utilizing this material as the cathode is determined to be excellent. Both the layered-layered-spinel composite structure and the nanoarchitecture morphology contribute to the electrochemical performance advantage of this material over other cathode materials.