A simple 1,1′-bi-2-naphthol (1,1′-BINOL) boron complex has been rationally designed and synthesized, the structure of which was confirmed by single crystal X-ray diffraction analysis. Furthermore, the complex exhibited turn-on fluorescence for fluoride ions with high selectivity and sensitivity. The recognition mechanism for promoting was determined by 1H, 19F and 11B NMR titrations, which indicated that both the photo-induced electron-transfer (PET) and the intramolecular charge transfer (ICT) effects were functionalized. In addition, the complex showed strong solid-state fluorescence, and the emission spectrum and quantum efficiency (ΦF) of the solid powders were also measured.