Aluminum toxicity in biological systems is a well-known issue yet remains as a prevalent and unsolvable problem due to the lack of proper molecular tools that can detect free aluminum(iii) or Al(iii) ions in vivo. Herein, we report a water-soluble photo-induced electron transfer (PET)-based turn-ON/OFF fluorometric chemosensor for the dual detection of Al(iii) and fluoride ions in aqueous media with a nanomolar (∼1.7 × 10-9 M) and picomolar (∼2 × 10-12 M, lowest ever detection so far) detection limit, respectively. Fluoride ions in sea water could be detected as well as the recognition of non-contamination in drinking water. In addition, using live-cell microscopy, Al(iii) ions were detected in live biological samples in vivo to aid establishing the aluminum-toxicity effect.