Electroluminescence from n-type porous silicon can be generated in solution by reduction of peroxodisulfate. It has been assumed that the SO4•- radical ion, formed in the first reduction step, injects a hole into the valence band of the porous semiconductor. The hole should subsequently undergo radiative recombination with a conduction band electron. Using two techniques, viz., photocurrent quantum efficiency measurements with p-type porous and crystalline silicon electrodes and minority carrier injection studies with the “transistor technique”, we found that the reduction of peroxodisulfate is, however, not always accompanied by hole injection. The silicon results are compared with results obtained on GaAs electrodes.