The development of low-cost and high-performance electrocatalyst-supporting materials is desirable and necessary for the ethanol oxidation reaction (EOR). Here, we report a facile and universal template-free approach for the first time to synthesize three-dimensional (3D) flower-like ionic liquid-functionalized graphene (IL-RGO). Then, the crystalline Pd nanoparticles were anchored on IL-RGO by a simple wet chemical growth method without a surfactant (denoted as Pd/IL-RGO). In particular, the IL is conducive to form a 3D flower-like structure. The optimized Pd/IL-RGO-2 presents a much-promoted electrocatalytic performance toward the EOR compared with commercial Pd/C catalysts, which is mainly derived from the grafted IL on RGO and the unique 3D flower-like structure. In detail, the IL can control, stabilize, and disperse the Pd nanocrystals as well as serving as the solvent and electrolyte in the microenvironment of the EOR, and the 3D flower-like structure endows the Pd/IL-RGO with high surface areas and rich opened channels, thereby kinetically accelerating the charge/mass transfers. Furthermore, density functional theory calculations reveal that the strong electronic interaction between Pd and IL-RGO generates a downshift of dcenter for Pd and thereby enhances the durability toward CO-like intermediates and electrocatalytic reaction kinetics.