In this work, temperature-responsive poly(N-isopropylacrylamide) (PNIPAM) and the guanylthiourea (GLA) were used to modify chitosan (CS) to prepare a novel PNIPAM/GLA/CS adsorbent for Ag(I) ions. Temperature variations near the lower critical solution temperature (LCST) facilitate the adjustment of functional group distribution within the composite material, thereby influencing its adsorption performance for silver ions. The characteristics of this composite material were confirmed using a variety of techniques, including scanning electron microscopy (SEM), variable-temperature ultraviolet-visible near-infrared spectroscopy, Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Studies on the adsorption of Ag(I) ions by the PNIPAM/GLA/CS adsorbent indicated that the optimal pH for adsorption is 6.0. The adsorption kinetics were best described by the pseudo-second order kinetic model, while the equilibrium adsorption data aligned more closely with the Langmuir adsorption isotherm model, achieving a maximum adsorption capacity of 336.33 mg/g at 40°C. Experimental results demonstrated that higher adsorption amounts were observed above the LCST, while desorption of target ions was more favorable below the LCST. This research provides valuable insights for the design of new structural adsorbents.