A pyrene-containing single-molecule excimer-emitting compound, 1,8-bis(pyren-2-yl)naphthalene (BPyN), was synthesized. With BPyN as a host emitter, C545T-based green OLEDs were fabricated, exhibiting high efficiencies of 22 lm W(-1), 22 cd A(-1) and 6.2% external quantum efficiency (EQE) at 100 cd m(-2), and 19 lm W(-1), 22 cd A(-1) and 6.2% EQE at 1000 cd m(-2).