Two structurally unique aggregation induced emission (AIE)‐active luminogens have been designed and synthesized based on the furocarbazole skeleton. Such small molecule AIEgens were designed based on forbidden planarity and engineering a twist into the scaffold to realize induction of emission in the aggregated states. The structures were fully characterized and their thermal stabilities, electronic properties, photophysical and electrochemical properties were systematically investigated. The unique twist in the molecules as evident from their X‐ray crystal structure along with the short intermolecular interactions enhances the structural rigidification and restricts detrimental π–π stacking interactions, restricting the internal rotations (RIR) accompanied by a curb of the ICT process, resulting in enhanced emission in the aggregated state. This intriguing luminescent property enabled one of the luminogens to selectively detect trinitrophenol (TNP) over other nitroaromatics in both aqueous and organic media at nanomolar concentrations. Moreover, the good photostabilities and biocompatibilities empowered both luminogens to function as fluorescent bioprobes for cancer cell imaging.