We report the electroluminescent (EL) characteristics of a new class of polymeric material, polysilanes, which were employed in Light-emitting diodes (LEDs) as an emissive material. In contrast to the LEDs utilizing pi-conjugated polymers and small molecules that have been reported to date, LEDs made from polysilanes exhibit EL in the near-ultraviolet (NUV) or ultraviolet (NUV) region due to their sigma-conjugation. Three types of polysilanes, dialkyl, monoalkyl-aryl and diaryl polysilanes, have been used as the emissive material, together with an indiumtin-oxide (ITO) and metal electrode for the injection of holes and electrons, respectively. The LED characteristics were observed to depend strongly on the chemical, optical and electronic properties of the emissive polysilanes. The development of emissive polysilanes has led to the successful fabrication of single-layer LEDs which emit NUV light at 107 nm (3.05 eV) with a quantum efficiency of 0.1% photons/electron at room temperature.