In this paper, the moderately and lightly doped porous silicon nanowires (PSiNWs) were fabricated by the ‘one-pot procedure’ metal-assisted chemical etching (MACE) method in the HF/H₂O₂/AgNO₃ system at room temperature. The effects of H₂O₂ concentration on the nanostructure of silicon nanowires (SiNWs) were investigated. The experimental results indicate that porous structure can be introduced by the addition of H₂O₂ and the pore structure could be controlled by adjusting the concentration of H₂O₂. The H₂O₂ species replaces Ag⁺ as the oxidant and the Ag nanoparticles work as catalyst during the etching. And the concentration of H₂O₂ influences the nucleation and motility of Ag particles, which leads to formation of different porous structure within the nanowires. A mechanism based on the lateral etching which is catalyzed by Ag particles under the motivation by H₂O₂ reduction is proposed to explain the PSiNWs formation.