Poor cycling performance and rate capability are the major barriers to the application of layered transition-metal sulfide as the next generation anodes materials for lithium-ion batteries (LIBs). In this paper, a smart composite consisting of defect-rich MoS2/carbon-coated ultrathin TiO2/defect-rich MoS2 sandwich-like nanosheets has been constructed to enhance the cycling and rate performances of MoS2. In this uniform sandwich-like structure, carbon-coated ultrathin TiO2 is conformably embedded by defect-rich MoS2 shells via intimate interfacial contacts, while the carbon coats TiO2 via Ti–O–C bonds. It is first revealed that the synergistic effect between rich defect in few-layer MoS2 nanosheets and abundant interfaces in the composites, as well as the high structure stability of TiO2 during discharge and charge process, results in excellent performance of the composites as LIBs anode materials. These LIBs anodes achieve the best rate capability (785.9, 507.6 and 792.3mAhg−1 at 0.1, 2 and 0.1Ag−1, respectively) and cycling performance (805.3mAhg−1 at 0.1Ag−1 after 100 cycles) among the TiO2 supported MoS2 based composites reported previous. The synergistic strategy can be expected to benefit the rational design of other anode materials for high-performance LIBs.