Metallic and alloyed powders were prepared with a novel technique, called electrostatic spray reductive precipitation (ESRP). This technique combines aerosol generation by electric means together with chemical precipitation in order to form solid particles with tunable features. The structural and compositional characterizations of Co, Sn and Co–Sn materials show that metallic and alloyed nanoparticles can be obtained. This synthesis method represents a new route to produce metal, alloyed and intermetallic particles, which here are considered as alternative anode materials for rechargeable Li-ion batteries. This approach, however, can be easily extended to the fabrication of other materials, enabling a wider range of applications e.g. for catalysis and hydrogen storage.