Oxabenzonorbornadienes were found to be suitable substrates for asymmetric hydroalkynylation reactions. Catalyzed by the complex of [Ir(COD)Cl](2) and (R)-SYNPHOS, oxabenzonorbornadienes and terminal alkynes could react smoothly to give the alkynylated products in moderate to good yields (up to 93% yield) and enantioselectivities (up to 85% ee).