A multifunctional fluorescent sensor based on a cyclen-appended BINOL derivative (R-1) was synthesized and characterized. It can display on-off-type fluorescence change with high selectivity toward Cu(II) among 19 metal ions in 100% aqueous solution. Furthermore, the in situ generated R-1-Cu(II) ensemble could recover the quenched fluorescence upon the addition of sulfide anion resulting in a off-on-type sensing with a detection limit of micromolar range in the same medium. No interference was observed from other biothiols and anions, including GSH, l-Cys, DTT, and sulfates, making it a highly sensitive and selective sulfide probe.