Several functional polystyrene-supported metal (Ru, Rh, Pd) catalysts were synthesized. The hydrogenation selectivity of these catalysts for polyunsaturated cycloolefines (1,5,9-cyclododecatriene, cyclopentadiene) and unsaturated carbonyl compounds (mesityl oxide, crotonaldehyde acrylic aldehyde) was investigated. Some important factors (pore size, crosslinkage of polymer supports, donor atoms and substituents thereon) for the tailoring of supports and ligands which have great influence over the hydrogenation selectivity of the supported metal catalysts are discussed.