A perylene bisimide derivative (PBI) based colorimetric and fluorescent bifunctional probe PAM-PBI was designed and synthesized. It was highly selective and sensitive for distinguishing both Cu2+ and F− from other ions through a conspicuous change of UV–vis and fluorescence spectra. The recognition of Cu2+ by PAM-PBI showed an obvious color change from rose red to purple in aqueous solution, while the sensing of F− gave a marked color change from rose red to light green in THF.