Hydrogenation of triple bond of dehydrolinalool to double one of linalool was studied with Pd colloids prepared in polystyrene-poly-4-vinylpyridine micelles in toluene and deposited on Al2O3. The high selectivity (99.8%) of this catalyst is explained by durable modification of the Pd nanoparticle surface with 4-vinylpyridine units. The activity of Pd catalyst studied is determined by high reactivity of small Pd nanoparticles. The influence of solvent nature on catalytic properties of Pd colloidal catalyst is studied. Maximum relative rate was found to be in methanol, but the highest selectivity was achieved in toluene because the latter is a selective solvent for polystyrene-poly-4-vinylpyridine micelles and provides the better accessibility of reactive sites.