Mesoporous smectite-type materials (SM) were synthesized with a hydrothermal method from water glass, magnesium chloride and alkyl ammonium salt. The mesopore diameter of SM was controlled from 30 to 130 Angstrom by changing the reaction temperature, pH and the template materials during hydrothermal treatment. Palladium metal particles were intercalated in the mesopores of SM with an ion-exchanging of [Pd(NH3)(4)Cl-2] on them and hydrogen reduction treatment. The size-selective hydrogenation of butadiene-acrylonitrile rubbers (NBR) in carbon tetrachloride was studied using palladium loaded smectite catalysts (Pd-SM). The reaction was controlled by the sizes of mesopore of Pd-SM, which determine the diffusion of polymer molecules onto the dispersed palladium particles within the pores.