Solar cells and optical detection devices often incorporate antireflective surfaces to reduce undesired reflection and enhance optical absorption. This letter reports a “black silicon” structure of antireflective porous silicon fabricated by using electrochemical etching. The sample has a gradient-index multilayer structure, i.e., the refraction indices of the structure increase from the top (near the air) to the bottom (near the Si substrate). Reflectance below 5% is obtained over a broad wave number range (3000–28000cm−1) and the depression mechanism of the optical reflectance is analyzed by simulating the structure with the transfer matrix method. The simulated result fits the measured spectra well.