The regioselective silylation of the alpha-C(sp(3))-H bond in the 2-alkyl group in 2-alkyl-1,3-azole derivatives with hydrosilanes, catalyzed by the combination of ((POCOPBu)-Bu-t)IrHCl and NaBAr4F, leading to the production of 2-(1-silylalkyl)-1,3-azoles is described. The presence of 3,5-dimethylpyridine is required for the reaction to procced. Although the reaction takes place both in the presence and absence of a hydrogen acceptor, the addition of an acceptor gave better results, in terms of the efficiency of the reaction.