Porosities of porous silicon layers formed on different types of substrates and under different experimental conditions are compared with and related to the pore size distribution determined by gas adsorption experiments. Results show that porous layers formed on lightly P‐doped silicon exhibit a network of very narrow pores, of radii less than 2 nm. Porous films formed on heavily doped silicon present larger radii, ranging between 2 and 9 nm according to the experimental conditions. Larger porosities and larger pore sizes are obtained by increasing the forming current density or by decreasing the concentration. Heavily P‐doped porous silicon layers are homogeneous in depth and generally present a quite sharp pore size distribution. With heavily N‐doped silicon, an increase in porosity with increasing thickness is found, which corresponds to an increase in pore size, leading to a broadening of size distributions. This porosity gradient is attributed to a chemical dissolution of the layer occurring during anodization. In addition, a strong dependence of porosity with small variations in doping level is found.