Dielectric measurements accompanied by infrared absorption and photoluminescence (PL) spectroscopy were used to investigate the electrical and optical properties of oxidized porous silicon (PS). As opposed to non-oxidized PS, only high temperature relaxation processes could be resolved for oxidized PS. Two relaxation processes have been observed. The first process is related to dc-conductivity that dominates at high temperatures and low frequencies. After subtraction of dc-conductivity we could analyse a second high-temperature relaxation process that is related to interface polarization induced by charge carriers trapped at the host matrix–pore interfaces. We found that, while the main effect of the oxidation on the PL appears to be a size reduction in the silicon nanocrystals that gives rise to a blue shift of the PL spectrum, its main contribution to the dielectric properties turns out to be blocking of transport channels in the host tissue and activation of hopping conductivity between silicon nanocrystals.