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The aim of this work was to incorporate a hydrophobic compound benzophenone (BP) into core–shell nanoparticles (NPs) and to study its release. The core of these NPs is based on polylactic acid (PLA) and serves as a nanocontainer to accommodate BP. The shell is constituted of a β-cyclodextrin polymer (Poly-β-CD) which ensures the control of BP release through non-covalent host–guest interactions. Studies were focused on the preparation, physico-chemical analysis of the BP-loaded NPs and on the elucidation of the release mechanisms. The main features which are the slow kinetics, the dilution-induced release and the total release of encapsulated BP are in good agreement with a mechanism mainly controlled by diffusion of BP and by its binding with the β-CDs cavities present at the surface of NPs.