Optically active (+)-bornyl- and (−)-menthylammonium platinates were synthesized starting from H2[PtCl6] · 4H2O and hydrochlorides of the corresponding amines. Catalytic activity of the complexes in the hydrosilylation reactions of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane with 1,1,3,3-tetramethyldisiloxane and acetophenone with diphenylsilane was studied. The addition of the siloxanes leads to a predominant formation of β-adduct. Activity of the catalysts, evaluated on the 50% conversion of the substrate, decreases in the following sequence: (−)-(menthylNH3)2[PtCl6] > (Et3NH)2[PtCl6] > (+)-(bornylNH3)2[PtCl4] > (+)-(bornylNH3)2[PtCl6]. Asymmetric induction is observed in the hydrosilylation of aceto-phenone in the presence of (+)-(bornylNH3)2[PtCl n ] (n = 4, 6); (+)-(bornylNH3)2[PtCl6] showed the highest catalytic activity and selectivity. The hydrosilylation of acetophenone gave 1-phenylethoxy(diphenyl)silane, 1-phenylvinyloxy(diphenyl)silane, and 2-phenylethyl-2-diphenylsiloxy(diphenyl)silane as the products.