Stereoselective isomerization of α-alkyl styrenes is accomplished using a new iron catalyst supported by phosphine-pyridine-oxazoline (PPO) ligand.The protocol provides an atom-efficient and operationally simple approach to trisubstituted alkenes in high yields with excellent regio-and stereoselectivities under mild conditions.The results of deuterium-labelling and radical trap experiments are consistent with an iron-hydride pathway involving reversible alkene insertion and β-H elimination.