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The palladium-catalyzed selective activation of CH bonds is of great importance for the construction of diverse bioactive molecules. Herein, monodisperse CuPd alloy nanoparticles supported on reduced graphene oxide have been used as high efficient and recyclable catalyst for C(sp3)−H acyloxylation of 8-methylquinolines in good yields under mild conditions. The developed catalytic system proceeds with low palladium loading, good catalyst recyclability, high step and atom efficiency, excellent chemo and regioselectivity, good substrate and functional group compatibility, and applicable for large scale up synthesis. Preliminary studies were carried out to gain insights into the heterogeneous catalysis mechanism.