A polyol method was first employed to synthesize MoS2@MWNT nano-flower composites. Due to their high conductivity, large aspect ratio and sharp edges, an excellent field emission performance was obtained relative to pure MoS2 with the turn-on field decreasing from 5.3 V μm−1 to 2.7 V μm−1 and the threshold field decreasing from 8.0 V μm−1 to 5.3 V μm−1. When used as anode materials for Li-ion batteries in an aqueous electrolyte, the composites exhibit a highest specific capacity of 1217 mA h g−1 at a current of 100 mA g−1, excellent cycling stability and high-rate capability, and a high specific capacity of 851 mA h g−1, which was still retained at a high current density of 1600 mA g−1.