A new thiacalix[4]arene phenothiazine derivative(2) based on a thiacalix[4]crown with a 1,3-alternate conformation has been synthesized and characterized. In THF-water mixture, Compound 2 exhibits a strong fluorescence emission, with a large Stokes shift(λex/em = 357 nm/505 nm, Δλ = 148 nm), which helps to avoid interference in excitation and emission. For the metal ions tested, the fluorescence of Compound 2 was quenched only by Fe3+ and Cr3+ ions. Evidence for the hydrolysis reaction promoted by the metal ions is given by X-ray crystallography, mass spectra(MS), infrared(IR) spectra, and fluorescence spectroscopy data. A new thiacalix [4] arene phenothiazine derivative (2) based on a thiacalix [4] crown with a 1,3-alternate conformation has been synthesized and characterized. In THF-water mixture, Compound 2 exhibits a strong fluorescence emission, with a Large Stokes Shift (λex / em = 357 nm / 505 nm, Δλ = 148 nm), which helps to avoid interference in excitation and emission. The fluorescence of Compound 2 was quenched only by Fe3 + and Cr3 + ions. Evidence for the hydrolysis reaction promoted by the metal ions is given by X-ray crystallography, mass spectra (MS), infrared (IR) spectra, and fluorescence spectroscopy data.