The synthesis of functionalized siloles has been a challenge because of the incompatibility of polar functional groups with the reactive intermediates in the conventional protocols for silole synthesis. In this work, a synthetic route for silole functionalization is elaborated, through which a series of functionalized siloles are successfully prepared. Whereas light emissions of traditional luminophores are often quenched by aggregation, most of the functionalized siloles show an exactly opposite phenomenon of aggregation-induced emission (AIE). The siloles are nonemissive when dissolved in their good solvents but become highly luminescent when aggregated in their poor solvents or in the solid state. Manipulation of the aggregation-deaggregation processes of the siloles enables them to play two seemly antagonistic roles and work as both excellent quenchers and efficient emitters. The AIE effect endows the siloles with multifacted functionalities, including fluorescence quenching, pH sensing, explosive detection, and biological probing. The sensing processes are very sensitive (with detection limit down to 0.1 ppm) and highly selective (with capability of discriminating among different kinds of ions, explosives, proteins, DNAs, and RNAs). The siloles also serve as active layers in the fabrication of electroluminescent devices and as photosensitive films in the generation of fluorescence patterns.