The hierarchical MoS2/carbonaceous materials composites have received considerable interest for electrochemical energy storage and conversion. In the present work, the hierarchical MoS2@RGO nanosheets, where ultrathin MoS2 nanosheets perpendicularly anchor on both sides of RGO, are successfully synthesized by a new route. Such hybrid structures not only improve the conductivity of the hybrid structure and effectively prevent the aggregation of MoS2 nanosheets, but also maximize the MoS2 loading in the MoS2@RGO composites to be over 92%. The formation process for the hierarchical MoS2@RGO nanosheets is also investigated. When evaluated as an anode material for sodium-ion batteries, the hierarchical MoS2@RGO nanosheets deliver an excellent cycling performance and a high specific capacity of 420 mA h g−1 at a current density of 100 mA g−1. The strategy can be used to prepare other hierarchical metal sulfides@RGO nanosheets as high performance anode materials for sodium-ion batteries.