Robust self-assembly with very high order is demonstrated by polyisobutylene-block-poly(ethylene oxide) (PIB-PEO) copolymers tailor-made by combining living cationic and anionic polymerization. A cubic micellar phase with long-range order and a glassy phase consisting of deformed spheroids are identified. Application of PIB-PEO in the synthesis of porous titanium oxide yields perfect anatase crystalline films with high regularity (see Figure).