We report the hydrogenation of furfural (FF) to furfuryl alcohol (FA) with Pd-containing catalysts stabilized by hypercrosslinked polystyrene (HPS). FF is one of the major ingredients of biooil produced by biomass pyrolysis, while FA is a source of value-added chemicals, thus, creating an effective path from biomass to important compounds. Different palladium precursors (PdCl2(CH3CN)2, Pd(CH3COO)2) were used for the catalysts synthesis. The nature of the precursor influences the size of palladium nanoparticles. The TEM and SAXS data showed that when using PdCl2(CH3CN)2, a monomodal distribution of particles size with mean diameter 5.4 ± 1.2 nm was observed, whereas for Pd(CH3COO)2, multimodal particle size distribution with the mean particle sizes up to 13.8 ± 5.4 nm was observed. The comparison of the catalytic activities of Pd-containing catalysts indicated that the more disperse sample of palladium showed higher values of FF conversion and selectivity to FA because of small particles.