A rare and rigid bis(salamo)-like sensor H4L was designed and synthesized with double N2O2-donors for coordination with metal ions and active sites for interaction with anions. The fluorescence intensity of the sensor H4L was measured for different solvents and water contents, and the best test system was selected. The symmetric bis(salamo)-like sensor H4L can be used to recognize Cu2+ and HSO4− with no interference from other ions. The association constant values (Ka = 3.9 × 102 M−1 and 3.5 × 106 M−1), limits of detection (LOD = 3.3691 × 10−7 M and 4.9787 × 10−7 M) and limits of quantification (LOQ = 1.1230 × 10−6 M and 1.6597 × 10−6 M) for sensor recognition of Cu2+ and HSO4− were calculated. Theoretical calculations were performed on the sensor molecule H4L and the complex is formed by the sensor H4L and Cu2+. Finally, the sensing mechanism was researched in detail.