Rechargeable lithium-ion batteries (LIBs) are widely used from portable electronics to electric vehicles. Silicon (Si) has been identified as one of the most promising anode candidates for the next-generation high-energy-density LIBs. Hierarchically Porous Silicon Anodes enable the reversible inward lithium breathing through the unique hierarchically porous structure. Such behavior is beneficial to maintain effective and robust transport pathways of electron and ions, as well as minimizing reactions between electrodes and electrolytes, which is critical to ensure batteries with high power and long cycling life. Lithium ion battery assembled with this new material shows high capacity (>1800 mAh/g), long cyclability and high coulombic efficiency, which are superior to the current commercial Si materials. The technology is compatible with the current slurry coating electrode fabrication process. It can also be extended to other advanced high-capacity anode materials such as tin, germanium and silicon alloy materials.