We report a method for synthesizing hierarchically structured tin–carbon (Sn–C) composites via aerosol spray pyrolysis. In this method, an aqueous precursor solution containing tin(II) chloride and sucrose is atomized, and the resultant aerosol droplets carried by an inert gas are pyrolyzed in a high-temperature tubular furnace. Owing to the unique combination of high reaction temperature and short reaction time, this method is able to achieve a hetero-structure in which small Sn particles (15 nm) are uniformly embedded in a secondary carbon particle. This procedure allows the size and size distribution of the primary Sn particles to be tuned, as well as control over the size of the secondary carbon particles by addition of polymeric surfactant in the precursor solution. When evaluated as anode materials for lithium-ion batteries, the resultant Sn–C composites demonstrate attractive electrochemical performance in terms of overall capacity, electrochemical stability, and coulombic efficiency.