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Antifouling polymer brushes are widely used to inhibit the formation of protein corona on nanoparticles (NPs) and subsequent accumulation in the liver and spleen. Herein, we demonstrate a θ-solvent-mediated method for the preparation of gold nanoparticles with a high polyethylene glycol (PEG) grafting density. Reaching the θ-solvent by adding salt (e.g., Na2SO4) can significantly increase the grafting density of the PEG brush to 2.08 chains/nm2. The PEG polymer brush prepared in the θ-solvent possesses a double-shell structure consistin