Porous silicon light-emitting diodes were found to emit strong line-shaped ultraviolet under a forward bias driving voltage of about 20 volts. The intensity was sufficiently strong to pump an organic crystal, Tb-dipicolinic acid, producing clear Tb 4f intra-shell transition photoluminescence spectrum. The current-voltage characteristics of the devices also showed negative differential resistance, which was frequency dependent. In addition, purging of the device with various gases could quench the electroluminescence but the intensity recovered partially after each purging, but with no change in emission spectrum. Both results indicate the transport was influenced strongly by local space charge. From the results, the electroluminescence mechanism is tentatively attributed to core recombination in the porous layer, and the spectral characteristics is due to the microcavity effect between the top Au contact and silicon substrate. The present study shows that porous silicon has the potential as UV source in optoelectronics applications.