Abstract In this work, a fluorescent probe (TPE‐DPA) with aggregation‐induced emission (AIE) characteristics was prepared for detecting pyrophosphate (PPi) by attaching a dipicolylamine (DPA) unit into tetraphenylethylene (TPE) group. TPE‐DPA exhibits intense green emission in aqueous media because of the formation of the nanoaggregates. In the presence of Cu 2+ , the emission of TPE‐DPA can be effectively quenched due to the formation of complex TPE‐DPA/Cu 2+ . However, upon addition of PPi, the fluorescence can be selectively recovered because of the higher affinity between Cu 2+ and PPi, and thus release of TPE‐DPA. The detection limit for PPi by using TPE‐DPA/Cu 2+ is as low as 56 nM. Importantly, this strategy can be utilized for real‐time monitoring the alkaline phosphatase (ALP) activity and for imaging of PPi in living cells.