Herein, aggregation-induced electrochemiluminescence (AIECL) of tetraphenylbenzosilole derivatives in an aqueous phase system with the participation of a co-reactant was systematically investigated for the first time. All organics that we studied exhibit excellent stability and dramatically enhanced electrochemiluminescence (ECL) and photoluminescence (PL) emission when the water fraction increases. The influence of substituents in the structure of tetraphenylbenzosilole derivatives on AIECL performance was proved by fluorescence, cyclic voltammetry, and related theoretical calculation. Among them, 2,3-bis(4-cyanophenyl)-1,1-diphenyl-benzosilole (TPBS-C) with strong electron-withdrawing cyano groups exhibits the best ECL behavior with the highest ECL efficiency (184.36%). The strongest ECL emission of TPBS-C not only stems from the aggregated molecules that restrict the intramolecular motion of peripheral phenyl groups, which inhibits the nonradiative transition, but also comes from the fact that TPBS-C has the lowest reduction potential, and twice the reduction process of TPBS-C occurs to produce more anion radicals (TPBS-C·-). Significantly, the ECL sensor based on TPBS-C nanoaggregates exhibits excellent detection performance for toxic Cr(VI) with a wide linear range from 10-12 to 10-4 M and an extremely low detection limit of 0.83 pM. This work developed an efficient luminophore with unique AIECL properties and realized the ultrasensitive detection of Cr(VI) in the aqueous phase system.