A highly efficient copper-catalyzed enantioselective ring opening of oxabicylic alkenes with Grignard reagents has been developed by using chiral spiro phosphine ligands. Excellent trans selectivities, good yields, and high enantioselectivities are obtained for a broad range of Grignard reagents under mild reaction conditions. The catalyst system shows an extraordinary activity and the TON of the reaction reaches 9000.