The liquid-phase stereoselective hydrogenation of phenyl alkyl acetylenics at 298 K and atmospheric pressure on Pd-supported catalysts has been studied. The catalysts were prepared by impregnation of Pd(acac)(2) precursor (1 wt% of Pd) on different siliceous substrates such as amorphous SiO2, mesoporous MCM-41 and silylated MCM-41. The poisoning effect of lead incorporation on the supported palladium was also studied. All the catalysts displayed high selectivity to cis-alkene isomer, with Pd/MCM-41 being the most active catalyst. Deliberately adding lead to the base, palladium catalysts underwent changes in the selectivity to cis-alkene isomer and a significant drop in the activity. All the solids were characterized by nitrogen adsorption - desorption isotherms at 77 K, TGA, TPR, H-2 and CO chemisorption, XRD, XPS, and TEM.