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The present work is focused on the understanding of the CeO2 support interactions with cyclodextrin‐stabilized palladium nanoparticles (PdNPs) and the effect in the Suzuki‐Miyaura reaction outcome. Mostly, it is evidenced the strong influence of the cyclodextrin torus on the reactivity of PdNPs towards the ceria matrix. Structural characterization by X‐rays photoelectron spectroscopy (XPS) Raman spectroscopy, diffuse reflectance spectroscopy (DRS) and powder X‐rays diffraction (XRD, via Rietveld refinement) afforded to infer that palladium is being partially brought into the CeO2 structure. Transmission electron microscopies (TEM and STEM) visualizations allowed to evidence a bimodal size distribution of PdNPs (1–5 nm and 20–100 nm) over the catalysts even though particles up to 5 nm are probably the most responsible for the catalytic results reported herein.