A series of macro cyclic multinucleating phenoxyimine ligands and the corresponding neutral binuclear (2-Ni-2) and trinuclear (3-Ni-3) nickel catalysts have been efficiently synthesized. The trinuclear nickel complex 3-Ni-3 showed high activity, high thermal stability, and slow chain transfer in ethylene polymerization, thus producing polyethylene with high molecular weight and low branch density. Highly regiospecific and isospecific polymerization of propylene was also achieved with 3-Ni-3, generating regioregular and highly isotactic propylene with high T-m, and crystallinity. This is the first example of regio-and stereo controlled propylene polymerization promoted by nickel phenoxyimine catalysts, Statistical analysis suggested selective 1,2-insertion and enantiomorphic site control mechanism in the chain propagation step, likely caused by the unique steric effect of macrocyclic ligands and the potential cooperative effect.