Four types of perylene diimide–amino acid derivatives (H₂PDIAla, H₂PDIGlu, H₂PDIPhe, H₂PDITyr) were chosen to interact with anions. The UV-vis, fluorescence (in DMF solution) and NMR spectra in DMSO-d₆ solution were studied. The results indicated that the four types of derivatives exhibit specific selectivity and high sensitivity for F⁻ and OH⁻ ions. The NMR titrations of the derivatives with F⁻ and OH⁻ ions confirmed the synergetic effect of hydrogen bonding and anion–π interaction between the derivatives and the anions (F⁻, OH⁻). In addition, we made a simple test-paper to develop its potential applications.