Devising sensors for the perrhenate anion in aqueous media is extremely challenging, and has seldom been reported in the literature. Herein, we report a fluorescence turn‐on sensor for the perrhenate anion in aqueous media based on the aggregation‐induced emission of a popular ultrafast molecular rotor dye, Thioflavin‐T. The selective response towards the perrhenate anion has been rationalized in terms of matching water affinity, with the weakly hydrated perrhenate anion spontaneously forming a contact ion pair with the weakly hydrated ultrafast molecule‐rotor‐based organic cation, Thioflavin‐T, which in turn leads to an aggregate assembly that provides a fluorescence turn‐on response towards perrhenate. The sensing response of Thioflavin‐T has been found to be quite selective towards the perrhenate anion when tested against anions that are ubiquitously present in the environment, such as chloride, nitrate, and sulfate anions. The formation of self‐assembled Thioflavin‐T aggregates has also been investigated by time‐resolved emission and temperature‐dependent measurements.