A novel highly sensitive colorimetric receptor trisphen for F- ion based on three-arm phenthroline derevative trisphen had been successfully designed, synthesized, and characterized. Experiments showed that receptor trisphen could selectively recognize the F- and AcO- in DMSO and even in competitive hydrogen-bonding mixture solutions. The ability of recognition and the bond between trisphen and anions were determined using naked eye, UV-vis, and fluorescence analyses. Benesi-Hildebrand equation indicated that receptor trisphen associated with F- and AcO- in a 1:2 stoichiometry. Moreover, H-1 NMR experiments were carried out to explore the insight of interaction between trishen and anions. To the best of our knowledge, this is the first example of anion sensor based on three-arm phenanthroline derivative.