A symmetrical diarylethene containing N-salicylideneaniline (Schiff base) units was synthesized. The structure was well confirmed by NMR spectroscopy, mass spectrometry, and elemental analysis. Its photochromism was investigated by UV/Vis absorption spectra and NMR. The result displayed that diarylethene can well perform photoisomerization, but no obvious intramolecular proton transfer was observed. Furthermore, we checked the effects of metal cations for the properties of N-salicylideneaniline-based diarylethene, which indicated that Cu2+ and Fe3+ cations can significantly affect the UV/Vis absorption spectra of diarylethene ring-open and ring-closed isomers.