A palladium-catalyzed asymmetric bis(alkoxycarbonylation) reaction of cyclic olefins in the presence of copper(l) triflate was achieved by using a chiral bioxazoline ligand under normal pressure of carbon monoxide and oxygen to give the corresponding optically active cis-dicarboxylates with enantio-selectivities up to 94% ee. The carbonylated product was well applied to the synthesis of a biologically active hexahydrobenz-[e]isoindole derivative.