Three-dimensional (3D) multilayer molybdenum disulfi de (MoS2)/reduced graphene oxide (RGO) nanocomposites are prepared by a solution-processed self-assembly based on the interaction using different sizes of MoS2 and GO nanosheets followed by in situ chemical reduction. 3D multilayer assemblies with MoS2 wrapped by large RGO nanosheets and good interface are observed by transmission electron microscopy. The interaction of Na+ ions with oxygen-containing groups of GO is also investigated. The measurement of lithium ion batteries (LIBs) shows that MoS2/RGO anode nanocomposite with a weight ratio of MoS2 to GO of 3:1 exhibits an excellent rate performance of 750 mAh g(-1) at 3 A g(-1) outperforming many previous studies and a high reversible capacity up to similar or equal to 1180 mAh g(-1) after 80 cycles at 100 mA g(-1). Good rate performance and high capacity of MoS2/RGO with 3D unique layered-structures are attributed to the combined effects of continuous conductive networks of RGO, good interface facilitating charge transfer, and strong RGO sheets preventing the volume expansion. Results indicate that 3D multilayer MoS2/RGO prepared by a facile solution-processed assembly can be developed to be an excellent nanoarchitecture for high-performance LIBs.