Synthesis of 1,2-bis(pentafluorophenyl)-o-carborane and its arylthio-derivatives is reported. The regioselective arylthiolation was successfully achieved via nucleophilic aromatic substitution (SNAr) reaction. A series of bis(perfluoroaryl)-o-carboranes with various para-substituents showed strong multicolor emission in the solid-state (Φf up to 47%), suggesting an aggregation-induced emission (AIE) character in this motif.