Abstract: To study the self-assembly process of supramolecular hydrogel，we monitored the selfassembly process of glutathione-silver ion（GS-Ag（I））hydrogels by molecular fluorescence spectrometry. The results showed that when the concentration of GS-Ag（I）as a gel increased from 0 to 0. 008 mol/L， the fluorescence excitation wavelength of hydrogel shifted from 350 nm to 370 nm. The data of excitation wavelength showed that the critical concentration of the hydrogel is 0. 005 mol/L，which was also confirmed by the rheological data and fluorescence microscopy photo. When the gelator concentration reached 0. 005 mol/L，the hydrogels had self- assembled into filamentous threedimensional network and changed from Newtonian fluid to non-Newtonian fluid. Therefore，the selfassembly process of hydrogels can be directly monitored by molecular fluorescence spectrometry when the fluorescence excitation wavelength of the hydrogel shows a spectral red shift relative to the monomer gelator of the hydrogel.

Key words: supermolecular hydrogel, molecular fluorescence spectroscopy, self-assembly