A Gemini surfactant (N-dodecyl propylenediamine γ-diquaternium bromide) assisted hydrothermal route was presented for the facile synthesis of nanotile-like molybdenum disulfide/graphene (NTL-MoS2/G) hybrid. The effect of the Gemini surfactant on the microstructure and electrochemical lithium storage performance of the NTL-MoS2/G hybrid is investigated. It is found that MoS2 sheets in the hybrid display a nanotile-like morphology with 3–6 layers and are homogenously anchored on the surface of graphene. Due to their more edges, the nanotile-like MoS2 sheets facilitate lithium ion insertion/extraction and electrolyte access. The NTL-MoS2/G hybrid exhibits much higher reversible capacity with significantly enhanced cyclic stability and rate capability than the pristine MoS2. The improvement in electrochemical performances of the hybrid can also be contributed to the robust composite structure and synergistic effects between NTL-MoS2 and graphene sheets.