Series of polyethers with different configurations were synthesized from chiral BINOL and optical epichlorohydrin. The optical behavior of the obtained polyethers is evaluated with specific optical rotation, UV-vis spectroscopy, circular dichroism (CD) and fluorescence spectroscopy. Thermogravimetric analysis (TGA) reveals the polyethers a good thermal stability. The fluorescence responses of the chiral polyethers on chiral phenylalanine anion were investigated. The sensors (S,S)-4 and (R,R)-4 showed high enantioselective fluorescent sensing ability to phenylalanine anion. The value of enantiomeric fluorescence difference ratio (ef) reached to 6.29. (C) 2016 Elsevier Ltd. All rights reserved.