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The synthesis, optical, and ion-sensing characteristics of a novel compound, 1, which is based on a 2,5-di(thien-2-yl)pyrrole scaffold with a 15-crown-5 unit, are reported. It is noteworthy that 1 can be utilized for turn-off fluorimetric detection of Pb(II) ions. The fluorescence response is based on cation-mediated reductive photoinduced electron transfer.