A tetraphosphoramidite ligand was successfully applied to a Rh-catalyzed hydroformylation of various symmetrical and unsymmetrical alkynes to afford corresponding α,β-unsaturated aldehyde products in good to excellent yields (up to 97% yield). Excellent chemo- and regioselectivities and high activities (up to 20 000 TON) were achieved. The corresponding α,β-unsaturated aldehyde products can be transformed into many useful and important organic molecules, such as indenamine derivatives and lukianol pyrroles. This great performance makes the hydroformylation of alkynes highly practical with great potential.