The present investigation highlights a rhodamine-Band coumarin-based efficient probe that selectively detects Ga 3+ over other metal ions. The active pocket of the ligand for trapping the metal ions and the binding stoichiometry of its Ga 3+ complex were discovered by single-crystal X-ray diffraction (SC-XRD) analysis. This binding stoichiometry was further confirmed in the solution state by mass spectrometry and Job's plot. The detection limit was found to be at the nanomolar level. Pyrophosphate being a well-known quencher could easily quench the fluorescence intensity of the RC in the presence of Ga 3+ and reversibly recognize Ga 3+ in the solution. The spiro ring opening of the ligand after Ga 3+ insertion is proposed to be the principal mechanism for the turn-on fluorescence response. This ring opening was confirmed by SC-XRD data and nuclear magnetic resonance (NMR) titration experiments. Both ground-and excited-state calculations of the ligand and complex have been carried out to obtain information about their energy levels and to obtain the theoretical electronic spectra. Furthermore, the live-cell imaging of the probe only and the probe after the addition of Ga 3+ have been carried out in HaCaT cells and satisfactory responses were observed. Interestingly, with the help of this probe, Ga 3+ can be tracked inside the intracellular organelle such as lysosomes along with other regions of the cell. The article highlights a rhodamine−coumarin-based probe for the detection of Ga 3+ over other metal ions with a nanomolar level detection limit. Structural characterization of the ligand and its Ga 3+ complex was investigated by SC-XRD. Density functional theory (DFT) and time-dependent DFT (TD-DFT) studies were carried out to explore the excited-state energies and electronic spectra. The application of the probe for the detection of Ga 3+ in live cells has been explored, and positive responses were observed.