Hybrid Ru‐containing catalysts, based on poly(propylene imine) (PPI) dendrimers, immobilized in silica pores, were synthesized and characterized by transmission electron microscopy and X‐ray photoelectron spectroscopy. The synthesized Ru catalysts proved their efficiency in the selective hydrogenation of levulinic acid and its esters at 80 °C, 30 bar of H2, and 50 % volume substrate concentration in water. Quantitative yields of γ‐valerolactone were obtained for both micro‐ and mesoporous Ru catalysts within 2 h with catalytic activity as high as 1610 h−1. The reaction rate and selectivity on γ‐valerolactone were found to depend on several factors such as carrier structure, temperature, presence of water, and substrate/Ru ratio. The novelty of these hybrid materials is the presence of both weak acid (SiO2) and organic base centers (dendrimer amino groups), enhancing the dispersion of Ru nanoparticles. The presence of amino groups in the catalyst stabilizes the Ru nanoparticles during the synthesis and promotes the adsorption of levulinic acid on the surface of Ru nanoparticles during the reaction. Synthesized hybrid Ru catalysts can be reused several times without significant loss of activity.