Stimulus-responsive functional materials show broad applications in the fields of sensing, optical switching and energy conversion devices. Herein, a one-dimensional chain compound constructed from the electron-deficient rigid polypyridine ligand 2,4,6-tri(4-pyridyl)-1,3,5-triazine and electron-rich sulfate was successfully synthesized with reversibly electron transferred photochromic and photoluminescent behaviors. Second-harmonic generation (SHG) active behavior studies showed that the compound exhibit photomodulation of nonlinear optical property with an impressive high SHG-switching contrast (ca. 6 times) before and after light irradiation. Furthermore, this compound exhibited selectively vapochromic behavior in response to different amines, allowing its application in the visual recognition detector for specific amines. Based on the photochromic and photoluminescent property, applications in inkless printing and information encryption were successfully demonstrated. This work shows a facile way to obtain sulfate-based compounds with stimulus-responsive multifunctions, expanding the repertoire of multifaceted chromic materials for advanced visual chromic sensors.