Phenylalaninol enantiomers are one of the most important chiral compounds due to its presence in biologically active molecules and pharmaceutical products. In this paper, a novel chiral fluorescence polymer sensor incorporating (S)-BINOL and oligomeric aniline via a nucleophilic addition-elimination reaction is designed and synthesized. Polymer sensor exhibits "turn-off" fluorescence quenching response upon the addition of Hg2+, and "turn-on" moderate fluorescence enhancement behavior towards phenylalaninol enantiomers. Meanwhile, this kind of (S)-BINOL-based polymer sensor can exhibit highly selective enantioselective recognition response towards (L)-phenylalaninol upon the addition of Hg2+ and the value of ef can reach as high as 5.4, which can be attributed to the formation of in situ generated radical cation arisen from oligomeric aniline moiety by Hg2+ induction.