The first application of a RuHCl(CO)(PPh3)3-OAc catalytic system on the selective intermolecular mono C-H silylation of 2-aryl N-heterocycles using HSiEt3 as the silylating reagent has been described. This protocol features good functional group tolerance and high regioselectivity, and has potential for gram scale-up, which provides a convenient and practical pathway for the synthesis of versatile organosilane compounds. This catalytic system can also be applied to the silylation of challenging sp3 C-H bonds.