Rhodium amine complexes, RhCl(CO)₂[Et₂N(CH₂)₃Si(OCH₃)₃] (Rh–NEt₂), RhCl(CO)₂[H₂N(CH₂)₃Si(OC₂H₅)₃] (Rh–NH₂) and RhCl(COD)[H₂NCH₂CH₂NH(CH₂)₃Si(OCH₃)₃] (Rh(COD)(N–N)), were tethered to the silica-supported metal heterogeneous catalysts, M–SiO₂ (M=Pd, Ni, Au), to give the TCSM (tethered complex on supported metal) catalysts, Rh–NEt₂/M–SiO₂ (M=Pd, Ni, Au), Rh–NH₂/Pd–SiO₂ and Rh(COD)(N–N)/Pd–SiO₂. These TCSM catalysts exhibit activities, at 40°C and 1 atm of H₂ pressure, for the hydrogenation of arenes that are higher than those of the separate homogeneous rhodium amine complexes, the separate silica-supported metal heterogeneous catalysts or the rhodium complex catalysts tethered on just SiO₂. The activities of the TCSM catalysts are strongly affected by both the tethered rhodium amine complex and the SiO₂-supported metal. Among these TCSM catalysts, Rh–NEt₂/Pd–SiO₂ exhibits the highest activity for the hydrogenation of toluene; its maximum TOF is 7.2 mol H₂ (mol Rh min)^-1 while its TO is 1919 mol H₂ (mol Rh)^-1 during a 5 h period. IR(DRIFT) spectral studies of the TCSM catalysts before and after being used for the hydrogenation of toluene show that during the hydrogenation, the two CO ligands of Rh–NEt₂/M–SiO₂ (M=Pd, Ni, Au) are lost from the rhodium center. After standing in air for one month, Rh–NEt₂/Pd–SiO₂ becomes more active for the hydrogenation of toluene, but the activity of the air-aged Rh(COD)(N–N)/Pd–SiO₂ is lower than that of the fresh catalyst.