Porous sandwiched graphene/Si nanocomposites (PG-Si) are prepared by in situ hydrolysis of tetraethoxysilane within the confined gallery region of graphite oxide, and then magnesium thermal reduction of the intra-gallery SiO2 to Si nanocrystals. The Si nanostructures are in situ formed within the confined gallery region of graphite, and they are compactly sandwiched between two neighboring graphene sheets. This compactly sandwiched structure affords enhanced electron conductivity, and prevents Si nanoparticles from aggregation. Meanwhile, the free voids between neighboring Si nanocrystals alleviate the volume change of Si during cycling. As a consequence, the resulting PG-Si nanocomposites are high-performance anode materials for lithium-ion batteries which show long cycle life (>500 cycles) and high specific charge capacity (1464mAhg−1 at a current density of 200mA/g, 920mAhg−1 at a current density of 1.68A/g after 500 cycles). The Li+ diffusion kinetics in PG-Si is also discussed.