A highly chemoselective and enantioselective fluorescent probe has been discovered for the recognition of prolinol among various primary and secondary amine-based amino alcohols. The mechanistic studies including 1D and 2D 1H/13C NMR and mass spectroscopic analyses and DFT calculations have shown that the aldehyde group of the probe can react with prolinol to generate a bicyclic oxazolidine unit which, through a possible intramolecular hydrogen bond interaction, will lead to highly selective fluorescence enhancement.