The phosphine oxide-catalyzed asymmetric intramolecular aldol reactions of diketones were investigated. The combination of tetrachlorosilane and a chiral phosphine oxide catalyst promoted the acetyl-selective enolization of diketones, and the subsequent intramolecular aldol reaction occurred in an enantioselective manner. The introduction of two trimethylsilyl groups at the 4- and 4'-positions in BINAP dioxide catalyst improved the enantioselectivity. This reaction provides an effective synthetic method to access β-tertiary-hydroxy cyclohexanones in high yields and with high enantioselectivity.