Amorphous Si (a‐Si) shows potential advantages over crystalline Si (c‐Si) in lithium‐ion batteries, owing to its high lithiation potential and good tolerance to intrinsic strain/stress. Herein, porous a‐Si has been synthesized by a simple process, without the uses of dangerous or expensive reagents, sophisticated equipment, and strong acids that potential cause environment risks. These porous a‐Si particles exhibit excellent electrochemical performances, owing to their porous structure, amorphous nature, and surface modification. They deliver a capacity of 1025 mAh g−1 at 3 A g−1 after 700 cycles. Moreover, the reversible capacity after electrochemical activation, is quite stable throughout the cycling, resulting in a capacity retention about around 88 %. The direct comparison between a‐Si and c‐Si anodes clearly supports the advantages of a‐Si in lithium‐ion batteries.