We report how the metal cation and its counteranions cooperate in the complexation-based macrocyclic chemosensor to monitor the target metal ion via the specific coordination modes. The benzothiazolyl group bearing NO2S2-macrocycle L was synthesized, and its mercury(II) selectivity (for perchlorate salt) as a dual-probe channel (UV-vis and fluorescence) chemosensor exhibiting the largest blue shift and the fluorescence turn-off was observed. In the mercury(II) sensing with different anions, except ClO4- and NO3-, no responses for mercury(II) were observed with other anions such as Cl-, Br-, I-, SCN-, OAc-, and SO42-. A crystallographic approach for the mononuclear mercury(II) perchlorate complex [Hg(L)(ClO4)(2)]center dot 0.67CH(2)Cl(2) (1) and polymeric mercury(II) iodide complex [Hg(L)I-2](n) (2) revealed that the observed anion-controlled mercury(II) sensing in the fluorescence mainly stems from the endo- and exocoordination modes, depending on the anion coordinating ability, which induces either the Hg-N-tert bond formation or not. The detailed complexation process with mercury(II) perchlorate associated with the cation sensing was also monitored with the titration methods by UV-vis, fluorescence spectroscopy, and cold-spray ionization mass spectrometry.