A novel ratiometric fluorescent Hg(2+) detecting system was rationally developed based on the typical excited state intramolecular proton transfer (ESIPT) characteristic of the latent fluorophore, 2-(1-(p-tolyl)-1H-phenanthro[9,10-d]imidazol-2-yl)phenol (Pol) and the Hg(2+)-mediated cleavage of the vinyl group. The probe responds selectively to Hg(2+) over various other metal ions with a larger bathochromic shift (∼100 nm). The sensing mechanism was investigated in detail by fluorescence spectroscopy, NMR spectra and mass spectrometry. Taking advantage of the enhancement effect of dichloromethane on the ESIPT efficiency, a facile dichloromethane extraction was introduced in the process of detection of Hg(2+), which affords a high sensitivity for the probe with a detection limit of 7.8 × 10(-9) M for Hg(2+). By using the new strategy, the novel probe can be used for the detection of Hg(2+) in practical water samples with good recovery. Moreover, the probe was successfully applied to the fluorescence image of Hg(2+) in living cells. These results indicated that the probe and the proposed method have promising applications for Hg(2+) sensing in biological and environmental sciences.