Thin films of block copolymer-surfactant complexes which Consist of polystyrene-b-poly(ethylene oxide) (PS-b-PEO) with dodecylbenzenesulfonic acid (DBSA) hydrogen-bonded to the ether group in PEO blocks, are investigated and characterized by FT-IR, DSC, AFM. TEM, GISAXS, and GIWAXD. The films are solvent-annealed for obtaining controlled orientation and high degree of lateral order of the microdomains. Selective loading of low-mass surfactant into PEO domains leads to morphological transition over wide range of phase diagram in self-assembled nanostructure of block copolymer. In addition, the self-assembly of amphiphilic surfactants combined with block copolymer produces hierarchical structure with multiple length scales and different orientations in thin films. Elimination of surfactants from the complexes by selective solvent, on the other hand, produces various nanostructured materials depending on the amount Of surfactants added and microdomain orientation in thin films. Consequently, low-mass amphiphilic surfactants complexed with one component of block copolymer were shown to play multiple roles ranging from generation of hierarchical structures to production of nanoporous films and nano-objects thorough self-assembly and resultant phase behaviors.