Porous silicon–carbon (Si–C) composite materials have attracted a great deal of attention as high-performance anode materials for Li-ion batteries (LIBs), but their use suffers from the complex and limited synthetic routes for their preparation. Herein we demonstrate a scalable and nontoxic method to synthesize porous Si–C composite materials by means of simultaneous chemical etching of Si and carbon phases using alkaline solution. The resulting porous Si–C composite material showed greatly improved cycle performance, good rate capability, and high dimensional stability during cycling. Porous Si–C electrode showed an expansion of the height by about 22% after the first lithiation and only 16% after the first cycle. The material synthesis concept and scalable simultaneous etching approach presented here represent a means of improving the electrochemical properties of Si-based porous anode materials for use in commercial LIBs.