A new highly sensitive luminescent iridium(III) chemosensor, 1, was designed and synthesized for tandem detection of fluoride ions (F^–) and aluminum ions (Al³⁺). This sensor 1 exhibited obvious luminesce quenching by hydrogen bond interactions with F^–. In addition, the resulting 1-F complex can be further used to detect Al³⁺ through a luminesce enhancement. The detection limit (0.02 μM) of 1-F for Al³⁺ is far lower than the World Health Organization (7.41 μM) limit for drinking water. Importantly, chemosensor 1-F could be used to detect and quantify F^– and Al³⁺ reversibly. This sensor achieved rapid detection of two ions, which relies on only one probe.