Layered-layered type xLi2MnO3·(1−x)LiMnO2 (x = 0.91, 0.78, 0.67, 0.54, 0.42, and 0.32) nanorods with a diameter of 100–200 nm and length of 400–1000 nm are prepared through a pyrolysis reduction process of monoclinic Li2MnO3 (m-Li2MnO3) nanorods. All the synthesized xLi2MnO3·(1−x)LiMnO2 nanorods exhibit the main characteristic diffraction peaks of m-Li2MnO3 in addition to some weak peaks attributable to m-LiMnO2 especially for those composites with x < 0.67. When used as cathode material of Li-ion battery, those xLi2MnO3·(1−x)LiMnO2 nanorods show an initial charge/discharge profile similar to the Li-rich solid solution in the voltage window of 2.0–4.8 V. The m-LiMnO2 portion in those synthesized composites can significantly enhance the reversible capacity but lower the cyclic stability, while the m-Li2MnO3 portion can improve the cyclic stability due to its retardation effect of the layered-to-spinel transformation during the charge/discharge processes, and thus xLi2MnO3·(1−x)LiMnO2 nanorods with x = 0.54 exhibits the best cyclic and rate performance since it contains appropriate m-Li2MnO3/m-LiMnO2 contents to balance the reversible capacity and Jahn-Teller effect. The present findings demonstrate an effective strategy for the development of low-cost pure Mn-based Li-rich layered cathode materials with adjustable reversible capacity, cyclic and rate performance by tailoring the composition.