The use of magnesium fluoride support for ruthenium active phase allowed obtaining new catalysts of high activities in the hydrogenation of toluene and ortho-chloronitrobenzene. Ruthenium colloid catalysts (1 wt.% of Ru) were prepared by impregnation of the support with the earlier produced polyvinylpyrrolidone (PVP)-stabilized ruthenium colloids. The performances of the colloidal catalysts and those obtained by traditional impregnation were tested in the reactions of toluene hydrogenation to methylcyclohexane and selective hydrogenation of ortho-chloronitrobenzene (o-CNB) to ortho-chloroaniline (o-CAN). It was shown that the use of chemical reduction method allows obtaining highly monodisperse ruthenium nanoparticles of 1.6–2.6 nm in size. After reduction in hydrogen at 400oC, the colloidal ruthenium nanoparticles were found to strongly interact with MgF2 surface (SMSI), which decreased the catalyst ability to hydrogen chemisorption, but despite this, the colloid catalysts showed higher activity in o-CNB hydrogenation and higher selectivity to o-CAN than the traditional ones. It is supposed that their higher activity can be a result of high dispersion of Ru in colloid catalysts and the higher selectivity can be a consequence of the lower availability of hydrogen on the surface.