Sensor X is a turn-on sensor, which is applied in the fluorescence detection of Zn2+ ions. Its photophysical process is comprehensively investigated to clarify its weak fluorescence. With the aid of density functional theory (DFT) and time-dependent density functional theory (TDDFT), the potential energy surfaces (PES) of X on both ground and first excited states are studied. Excited-state intramolecular proton transfer (EPT) processes as well as molecule twisting motion are observed, which induces several minima on the excited-state PES. Transition states as well as rate constants for these dynamic processes are obtained to evaluate their occurrences. The twisting motion of the sensor is an ultrafast process, which is initiated by a specific EPT process and leads to a nonemissive twisted intramolecular charge transfer (TICT) state. The fluorescence of the sensor is barely observable because of the easily attainable TICT state on the excited PES. This mechanism is trustworthy and intrinsically different from the previously proposed mechanism. After clarifying the photophysical process of the sensor, the Zn2+ sensing mechanism is uncovered. Also, the selectivity against Cd2+ and Hg2+ is fully discussed.