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The paper explores the synthesis of oxide-free nanoparticles of Ag and Cu through laser ablation of pure targets under aqueous medium and tuning the quality and size through addition of Polyvinylpyrrolidone (PVP) in the medium. The size distribution of nanoparticles reduces from 37 ± 30 nm and 13 ± 5 nm to 32 ± 12 nm and 4 ± 1 nm for Ag and Cu with changes in PVP concentration from 0.00 to 0.02 M, respectively. Irregular shaped particles of Ag with Ag₂O phase and a Cu–Cu₂O core–shell particles form without the addition of PVP, while oxide layer is absent with 0.02 M of PVP. The recent understanding of the mechanism of particle formation during laser ablation under liquid medium allows us to rationalize our observation.