The rhodium(I) complexes [Rh(Cl)(COD)(R-NHC-(CH2)3Si(O iPr)3)] [COD=cyclooctadiene; R=2,6-diisopropylphenyl ( 1 a); n-butyl ( 1 b)] are effective catalyst precursors for the homogeneous hydrodechlorination of benzyl chloride using HSiEt3 as hydrogen source. This reaction is selective to the formation of toluene. However, in presence of a stoichiometric amount of potassium tert-butoxide (K tBuO) the formation of mixtures containing toluene together with 17-19 mol % of the CC homocoupling product, namely PhCH2CH2Ph, is observed. A mechanism proposal based on experimental insights and theoretical calculations at the DFT level that allows explanation of the experimental findings is included. Moreover, the heterogeneous catalytic system based on catalyst 1 a supported on MCM-41 has been demonstrated to be effective for the solvent-free hydrodechlorination of benzyl chloride using HSiEt3 and HSiMe(OSiMe3)2.