Poly(N-vinyl pyrrolidone) (PNVP)-grafted graphene oxide (GO) (GO-PNVP) has been synthesized using a GO-based macro-RAFT agent prepared via click reaction of alkyne-terminated RAFT agent (S)-2-(propynyl propionate)-(o-ethyl xanthate) and azide-functionalized GO (GO-N₃). FTIR, XPS, Raman, TGA and DSC studies confirmed its formation. Silver nanoparticles are then immobilized on GO-PNVP and GO via in situ reduction of silver nitrate in the presence and absence of glucose at 40 and 95 °C, respectively. FT-IR, UV-Vis, XRD, SEM and TGA studies supported the incorporation of silver (Ag) nanoparticles. Ag nanoparticles immobilized on GO-PNVP are small, spherical and narrowly distributed (homogenous, monodisperse) compared to GO. These nanocomposites are explored as catalysts for the reduction of p-nitrophenol into p-aminophenol and also as antibacterial agents towards Gram(+) S. aureus and Gram(−) E. coli bacteria. Ag nanoparticle immobilized GO-PNVP showed efficient catalytic activity and excellent reusability along with an excellent antibacterial activity. Hence, grafting of PNVP enhances the catalytic and antibacterial properties of GO.