An ew type of multistimuli-responsiveh ydrogels cross-linked by metal ions and biopolymers is reported. By mixing the biopolymer chitosan (CS) with av ariety of metal ions at the appropriate pH values,w eo btained as eries of transparent and stable hydrogels within afew seconds through supramolecular complexation. In particular,the CS-Ag hydrogel was chosen as the model and the gelation mechanism was revealed by various measurements.Itwas found that the facile association of Ag + ions with amino and hydroxy groups in CS chains promoted rapid gel-network formation. Interestingly, the CS-Ag hydrogel exhibits sharp phase transitions in response to multiple external stimuli, including pH value, chemical redox reactions,c ations,a nions,a nd neutral species. Furthermore,this soft matter showed aremarkable moldability to form shape-persistent, free-standing objects by af ast in situ gelation procedure.