A novel of Si/porous reduced graphene oxide (rGO) composite is fabricated by steam etching of Si/rGO aerogel. The rGO sheets with nano-holes build a unique three-dimensional porous network and can encapsulate the Si nanoparticles. The porous structure of Si/rGO composite can reduce the transfer distance of Li ions and restrain the aggregation and destruction of Si particles. The in-situ transmission electron microscopy (TEM) observation demonstrates that the porous rGO sheets help the entire electrode to maintain highly conductive and facilitate the lithiation of Si nanoparticles. The composite electrode presents high specific capacity and good cycling stability (1004 mAh g−1 at 50 mA g−1 up to 100 cycles).