We developed a simple method for the preparation of polyelectrolyte/silver nanocomposites, where silver nanoparticles were dispersed in a polyelectrolyte. Copoly(TEAMPS/VP)/silver (w/w=100/0, 100/1, 100/2, 100/3 and 100/4) nanocomposites were obtained by a thermal decomposition reaction of silver carbamate complex at 130 degrees C, and well-dispersed silver colloids were stabilized by copolymer of tetraethylammonium 2-acrylamido-2-methyl-1-propanesulfonate (TEAMPS) and N-vinylpyrrolidone (VP). A dark brown solution in its UV-vis absorption spectrum showed surface plasmon resonance absorption bands at 420 nm in solution. The silver precursor and the resulting polyelectrolyte/Ag nanocomposite was characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), infrared (IR), transmission electron microscopy (TEM). In addition the humidity-sensing properties using copoly(TEAMPS/VP)/Ag nanocomposite films were examined.