A novel series of emissive o-carborane derivatives, which showed multicolor, highly solid-state emission (ΦF ≥ 43%) and ideal photochemical stability, were synthesized. Inspired by the powerful mammalian olfactory system, we, for the first time, successfully obtained a fluorescent sensor array, which exhibits superior detection capability for nicotine in the gaseous phase (down to 3 ppb). Furthermore, the sensor array can be extended to detect nicotine in aqueous solution at the nano-gram level (∼0.1 ng cm-2) and determine the smoke of cigarette and electronic cigarette.