Nano-silver/polyvinylpyrrolidone (PVP) composite materials were synthesized in the silver nitrate solution containing PVP by microwave. The mechanism of catalytic reduction of sliver ion by atom N in PVP was discussed. UV-Vis and XRD results indicate the presence of nano silver with face-centered cubic structure. TEM result shows that nano silver particles with 15~25 nm size were homogeneously dispersed in the PVP matrix. XPS results suggest that there is an interaction between PVP and nano Ag.