Amorphous silicon (a-Si), due to its satisfactory theoretical capacity, moderate discharge potential, and abundant reserves, is treated as one of the most prospective materials for the anode of sodium-ion batteries (SIBs). However, the slow Na + diffusion kinetics, poor electrical conductivity, and rupture-prone structures of a-Si restrict its further development. In this work, a composite (a-Si@rGO) consisting of porous amorphous silicon hollow nanoboxes (a-Si HNBs) and reduced graphene oxide (rGO) is prepared. The a-Si HNBs are synthesized through "sodiothermic reduction" of silica hollow nanoboxes at a relatively low temperature, and the rGO is covered on the surface of the a-Si HNBs by electrostatic interaction. The as-synthesized composite anode applying in SIBs exhibits a high initial discharge capacity of 681.6 mAh g -1 at 100 mA g -1 , great stability over 2000 cycles at 800 mA g -1 , and superior rate performance (261.2, 176.8, 130.3, 98.4, and 73.3 mAh g -1 at 100, 400, 800, 1500, and 3000 mA g -1 , respectively). The excellent electrochemical properties are ascribed to synergistic action of the porous hollow nanostructure of a-Si and the rGO coating. This research not only offers an innovative synthetic means for the development of a-Si in various fields but also provides a practicable idea for the design of other alloy-type anodes.