Nano/micro-structured Si/CNT/C and Si-Cu/CNT/C microspheres are prepared by two simple steps of spray drying and carbonization, which are efficient and easy to scale up. In the Si/CNT/C composites, silicon particles (about 50–200nm) are covered by a layer of carbon formed by pyrolysis of phenol-formaldenhyde resin (PF), which, in turn, connects with the three-dimensional multiwall carbon nanotubes (MWCNTs) conductive network. Numerous open pores, which could buffer volume expansion of silicon and improve the electrode kinetics, are engendered in the microspheres due to the rapid evaporation of solvent and unfoldment of flexible MWCNTs. Moreover, introduction of small amount of copper (5wt.%) into the microspheres as Cu3Si phase reinforces the mechanical stability and improves the electronic conductivity. The favorable Si/CNT/C composite structure leads to significantly improved cycling stability and rate performance (ca. 1250mAhg−1 at 5Ag−1) compared to pristine Si particles. Addition of copper further enhances the capacity retention to 91.2% after 80 cycles.