PE-block-PS and P(E-co-P)-block-PS block copolymers were synthesised via sequential monomer addition during homogeneous polymerisation on various phenoxyimine catalysts. One phenoxyimine catalyst was tailored to produce high molecular weight block copolymers containing both, polyolefin and polystyrene segments. According to chromatographic analysis and TEM morphology studies, blends of block copolymers and PE homopolymers [or P(E-co-P), respectively] were formed. The direct olefin/styrene block copolymer synthesis on phenoxyimine catalysts represents an attractive, new one-pot route to styrenic block copolymers which are commercially prepared by anionic styrene/diene block copolymerisation followed by hydrogenation.