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This work is addressing the selective hydrogenation of alkynols over hybrid catalysts containing Pd-nanoparticles, within newly synthesized hyper-cross-linked polystyrenes (HPS). Alkynols containing C-5, C-10, and C-20 with a terminal triple bond, which are structural analogues or direct semi-products of fragrant substances and fat-soluble vitamins, have been studied. Selective hydrogenation was carried out in a batch mode (ambient hydrogen pressure, at 90 degrees C, in toluene solvent), using hybrid Pd catalysts with low metal content (less than 0.2 wt.%). The microporous and mesoporous HPS were both synthesized and used as supports in order to address the influence of porosity. Synthesized catalysts were shown to be active and selective: in the case of C-5, hydrogenation selectivity to the target product was more than 95%, at close to complete alkynol conversion. Mesoporous catalysts have shown some advantages in hydrogenation of long-chain alkynols.