Silicon shows photo-and electroluminescence at visible wavelengths when chemically etched into a microporous network of ＇wires＇ several nanometres thick(1). This raises the possibility of a silicon-based optoelectronic technology. The luminescence properties may be understood on the basis of the injection or creation of electrons and holes in the interconnected network of wires which recombine radiatively with high efficiency(1,2). Elucidating the electron-transport mechanisms has been held back by several difficulties, particularly that of making stable, high-quality contacts to the porous material. Here we report experiments that probe the conduction process using photoemission stimulated by hard-ultraviolet/X-ray synchrotron radiation, obviating the need for good electrical contacts. We find that the conductivity of porous silicon films is temperature-dependent, and that the films become insulating at low temperatures. We suggest that these results may be understood in terms of a percolation process occurring through sites in the porous network in which conductivity is thermally activated, and we postulate that this activation may be the consequence of a Coulomb blockade effect(3,4) in the nanoscale channels of the film. This is consistent with our observation of optical ＇unblocking＇ of conducting pathways. These results imply that the size distribution of the nanowires in the silicon backbone plays a key role in determining the conduction properties, and that porous-silicon light-emitting diodes may use only a small (and the least efficient) fraction of the material. Improvements in electroluminescence efficiency may be possible by taking into account the percolative nature of the conduction process.