A new double-salamo-type tetranuclear copper complex [Cu4(L)2](ClO4)2.2CH2Cl2 was designed and prepared, in which the metal atoms in the complex crystals have two different coordination systems, forming a symmetric structure as a whole. As a complex probe molecule, the addition of S2- in solution can achieve a red shift in the fluorescence spectrum, revealing bright green fluorescence, colorimetric and fluorescent dual-channel specific recognition ability and excellent anti-interference ability. The probe can be used to detect S2- by adding acidic and alkaline solutions to adjust the pH of the system for several cycles, which is suitable for ion recognition in most organisms and environments under pH conditions. The working mechanism of S2-recognition by Cu–ZTS was determined to be a synergistic action of ESIPT effect and ICT effect by correlation spectroscopy experiments, HR-MS and XPS tests, and this conclusion was subsequently further verified using theoretical calculations. Finally, the probe molecule showed good practical application value, and the portable test strips were prepared to qualitatively detect the ions, and by testing four different water samples, it was shown that the quantitative recognition of S2- could be realized almost without interference in real water samples. It proves that the coordination probe molecule has good prospects for practical application.