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Ag@C core–shell structures were prepared using hydrothermal methods by AgNO3 reduction with ascorbic acid in the presence of polyacrylamide (PAM). Temperature plays a key role in the formation of the core–shell structures. The roles of reactants, surfactant concentrations and reaction time on the morphologies of core–shell nanoparticles were investigated in detail. This synthetic method is one-pot synthesis, which is fast, high-yield and environmental-friendly for fabrication of Ag@C core–shell structures. The surface properties of core–shell Ag@C nanoparticles were characterized by Raman spectroscopy.