Reductive precipitation of Sn(II) chloride by NaBH4 is assisted by electrospraying in order to achieve a fine dispersion of the liquid precursor solution into the reductive bath. The formation of a highly charged aerosol of precursor droplets enables the size reduction of the constitutive units for the synthesized materials. Nanostructured Sn-based powders resulting from this process are tested as negative electrodes in Li cells. The presence of nanostructures has a significant influence on the cycling behaviour of the materials, which retained a capacity of about 300mAhg−1 after 100 cycles measured between 0.05 and 1.20V.