In order to selectively oxidize benzyl alcohol, a novel noble metal catalyst based on polymer ionic liquids with a core–shell structure was created. First, polymer ionic liquid microspheres (PILMs) were prepared by free radical polymerization. Second, the in situ adsorption of Au nanoparticles on the surface of PILMs was accomplished, thanks to the strong electrostatic interaction between N atoms and metal ions on the diazole ring of PILMs. Additionally, the introduction of Al(OH)3 prevented the aggregation of Au nanoparticles and promoted the catalytic reaction. Finally, the PILM/Au/Al(OH)3 catalyst with a core–shell structure was formed. The effectiveness of the PILM/Au/Al(OH)3 catalyst was assessed by varying the catalyst’s type, quantity, amount of Au, amount of H2O2, temperature, and reaction time. After five cycles of experiments, the catalyst was effective and reusable. In addition, the potential catalytic mechanism of the catalyst in the oxidation of benzyl alcohol was proposed.

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