Acylation of vinylsilanes with acid anhydrides is calalyzed by [RhCl(CO)(2)](2) to give alpha,beta-unsaturated ketones. The application of this catalytic system to the acylation of alpha-acyloxy vinylsilanes affords alpha-acyloxy enones in good yields, which are converted to unsymmetrical 1,2-diketones or their mono acetals.