A new class of cis-stilbene/fluorene spiro hybrid systems with paired diphenylamino donor and cyano, N-phenylbenzimidazole, dimesitylboranyl, or b,b-diphenylethenyl acceptor units was synthesized as ambipolar materials for organic light-emitting diode applications. When coupled with hole transporting 4,49-bis(1-naphthylphenylamino)-1,19-biphenyl (a-NPB) and electron transporting 2,29,299-(1,3,5-benzene-triyl)-tris(1-phenyl-1-H-benzimidazole) layers, they served as one of the best bluish green and pure green emitting layers with excellent external quantum efficiencies of 3.9–5.2%, electroluminescent brightness of 2202–3069 cd m 22 , luminance efficiencies of 11.0–15.8 cd A 21 , and power efficiencies of 5.7–6.6 lm W 21 at 20 mA cm 22 , which were about 2–3 times better than those based on standard a-NPB/tris(8-hydroxyquinoline)aluminum bilayer devices.