Highly efficient exciplex emission is observed from molecular organic light-emitting diodes (MOLEDs) based on silole derivatives as emissive and electron transport materials, and a hole transporting amine derivative. A silole derivative, 2,5-di-(3-biphenyl)-1,1-dimethyl- 3,4-diphenylsilacyclopentadiene (PPSPP), which shows blue fluorescence (476 nm) with a high solid-state photoluminescence quantum yield of 85% was used as the emitter. Another silole derivative, 2,5-bis-(2′,2″-bipyridin-6-yl)-1,1-dimethyl-3,4-diphenylsilacyclopentadiene which exhibits high electron mobility, was used as the electron transport material. MOLEDs using these two siloles and N,N′-diphenyl-N,N′-(2-napthyl)-(1,1′-phenyl)-4,4′-diamine (NPB) as the hole transporter show electroluminescence (EL) emission centered at 495 nm. This red-shifted EL band relative to the blue fluorescence of PPSPP is assigned to a NPB:PPSPP exciplex. An operating voltage of 4.5 V was measured at 100 cd/m2 and an EL quantum efficiency of 3.4% was achieved at 100 A/m2. © 2003 American Institute of Physics.