Heterogeneous Pd(0) catalysts were synthesized using bayberry tannin-grafted silica beads (BT-SiO2) as the supports, in which bayberry tannin acts as a stabilizer to prevent Pd(0) nanoparticles from aggregation as well as an antioxidant for keeping Pd(0) nanoparticles from oxidation. The main physical and chemical properties of the catalysts were characterized by Ultraviolet diffusion reflection spectra, X-ray diffraction, Transmission microscopy, and X-ray photoelectron spectroscopy. Experimental results indicated that Pd(0) nanoparticles stabilized by BT-SiO2 were highly active, selective and reusable in liquid-hydrogenation of unsaturated organic compounds.