A new class of N-pyrrolylphosphanes based on new heterocyclic amines have been synthesized, characterized and applied in homogeneous rhodium-catalyzed hydroformylation of 1-octene. These ligands possessing strong pi-acceptor properties effectively facilitate the olefin isomerization. The steric effect of ligands has also been examined. Large steric tetraphosphane ligand afforded better regioselectivity, and the L/B ratio of about 6.4 was obtained at low synthesis gas pressure (5 bar). New heterocyclic amines have been developed, and two type pyrrole-based ligands possessing strong pi-acceptor and weak -donor properties have been prepared. High regioselectivity has been achieved in the rhodium-catalyzed hydroformylation of terminal olefin.