In the presence of a simple combined catalyst of a tungstate monomer (TBA(2)WO(4), TBA: tetra-n-butylammonium) and rhodium acetate (Rh-2(OAc)(4)), hydrosilylation of various types of substances including ketone, aldehyde, carbon dioxide, alkene, nitrile, and furan derivatives efficiently proceeded, affording the corresponding hydrosilylation products in moderate to high yields (>= 63% yields). In addition, the present system was also applicable to the one-pot reduction of benzamide to benzylamine (95% yield).