In this study, we have successfully synthesized polystyrene-b-poly(4-hydroxystyrene) (SH) with molecular weight of 14k and with narrow molecular weight distribution by living anionic polymerization, and the obtained SH diblock copolymer has formed the definite alternative lamellar structure with the half pitch of 10.4nm. In order to achieve narrow half pitch pattern, diblock copolymer (XY) with stronger segregated polymer components with high chi (X and Y) was used, and it was confirmed that the high-chi XY diblock copolymer having molecular weight of 6k showed the clear lamellar structure with the half pitch of 5.5nm. Furthermore syntheses of multiblock copolymers with high chi such as YXY (where X is Si contained polymer) triblock and XYXY (where XYXY is Si contained high χ polymer) tetrablock copolymers were attempted to achieve the narrower half pitch pattern less than 5 nm, and the multiblock copolymers with aimed molecular weight and narrow molecular weight distribution have been successfully obtained. From the highchi multiblock copolymers, it was confirmed that the formation of the definite microphase-separated structure with the half pitch of 4.8nm was observed by TEM and SAXS measurements. Moreover we have developed a large-scale living anionic polymerization apparatus for the preparation of well-defined block copolymers scaled over 3kg.