Metal-assisted etching of silicon in HF/H₂O₂ aqueous solutions has been used to fabricate luminescent silicon nanowires (SiNWs) and porous silicon. The impact of the gold catalyst layer thickness and the etching solution on the morphology of the synthesized nanostructures and the diameter of the obtained nanowires were systematically investigated. Scanning electron microscopy (SEM) analyses reveal that the morphology of the fabricated structures strongly depends on the composition of the solution and the thickness of the catalyst layer. It has been observed that SiNWs are formed in solutions with H₂O₂ ratios (ξ) below 10 %; increasing the H ₂O₂ concentration above this critical value leads to mesoporous (10 % < ξ < 14 %) and macroporous (14 % < ξ < 17 %) structures. Photoluminescence measurements show that SiNWs emit light at about 430 nm. Fourier transform infrared (FTIR) spectroscopy and transmission electron microscopy (TEM) analyses were utilized to determine the origin of the emission in the silicon nanostructures. TEM imaging demonstrates that SiNWs are covered by a thin layer of porous silicon, which is assumed to be responsible for their light emission.