A series of bis(phenoxyketimine)titanium dichloride complexes were synthesized and screened for propylene polymerization activity when activated with methaluminoxane (MAO). Polymerizations of propylene by these catalysts in a living fashion furnished isotactic polypropylenes with narrow polydispersities. These catalyst systems were used for the synthesis of a number of unique block copolymers consisting of isotactic polypropylene and poly(ethylene-co-propylene) segments.