The present invention provides a series of diphenylimidazole-fused, spirally configured cis-stilbene/fluorene hybrid compounds and an optoelectronic device comprising the same. The diphenylimidazole-fused, spirally configured cis-stilbene/fluorene hybrid compound bearing cyanoaryl and cyanoheteroaryl substituents, and have glass transition temperatures ranged from 154° C. to 194° C., decomposition temperatures ranged from 426° C. to 443° C., reversible electron transport property, and balanced charges motilities. In addition, a variety of experimental data have proved that these diphenylimidazole-fused, spirally configured cis-stilbene/fluorene hybrid materials can indeed be used as a hole-blocking type electron-transporter for phosphorescent OLEDs.