The electrochemical formation of porous silicon (PS) layers in the n(+) emitter of silicon p-n(+) homojunctions for solar energy conversion has been investigated. During the electrochemical process under constant polarization, a variation of the current density occurs. This effect is explained by considering the doping impurity gradient in the emitter and by TEM characterization of the PS layer structure. Optical transmission measurements indicate that modifications of the refractive index and absorption coefficient of PS are mainly related to the porosity value. Reflectivity measurements, spectral response and I-V characteristics show that PS acts as an efficient antireflection coating layer. However, beyond a critical layer thickness, i.e. when PS reaches the p-n(+) interface, the junction properties are degraded.