Comparison diagram of flotation behavior of lepidolite by new Gemini collector HBDB and traditional monomolecular collector DA. • A novel amine-based Gemini surfactant HBDB was synthesized in our lab. • HBDB was introduced as an efficient collector of lepidolite flotation. • HBDB has better collecting ability and selectivity than traditional collector DA. • Using less dosage HBDB obtained a higher quality lepidolite concentrate. The global lithium supply and demand in this century is accelerated by the energy transition from carbon-based fossil fuels to renewable energy where electrical energy storage and electric vehicles heavily depend on the lithium-ion battery. The lepidolite is one of the main resources for extracting lithium, and it is usually enriched by froth flotation separation technology. However, the traditional lepidolite collector is monomer surfactant with only a single hydrophobic group and hydrophilic group, which usually leads to the low flotation separation efficiency. Therefore, to achieve the flotation separation of lepidolite ore more efficiently, in this work, an amine-based Gemini surfactant, hexanediyl-α, ω-bis (Dimethyldodecylammonium bromide) (HBDB), was synthesized, and compared with the conventional single molecule collector dodecylamine (DA). The experimental results show that the optimum pH value of flotation is 3, and the optimum dosage of HBDB and DA are 150 g/t and 300 g/t respectively. In bench-scale flotation experiments, compared with the conventional monomer DA collector (350 g/t), the Gemini HBDB with only 1/2 dosage of DA (175 g/t) increased the recovery of lepidolite by 16.18%. Economic calculation for a lepidolite ore plant, 1500 t/d, demonstrating that using Gemini HBDB can gain more about $ 8.2 million USD per year than using traditional unimolecular DA. Accordingly, this study provides a new and highly efficient collector for the flotation separation of lepidolite ore.