Solid-state complexes between diblock copolymer and amphiphilic surfactant (surf) results in polymers characterized by two length scales with one macroscopic ¡§block copolymer length¡¨ and one mesomorphic ordered ¡§nanoscale¡¨. In this study, the desired polymer was prepared by complexing the surf molecules, i.e., 4-dodecylbenzenesulfonic acid (DBSA), with polystyrene-block-poly(4-vinyl pyridine) (PS-b-P4VP) and a comb-coil A-block-(B-graft-C) type copolymer can be generated through a supramolecular assembly route. On the block copolymer scale, the PS blocks are phase-separation from the P4VP(DBSA)x block, which x denotes the molar ratio between DBSA and pyridine groups. Bonding interaction between PS-b-P4VP and DBSA was conformed by FTIR. PLM was used to detect the mesomorphic structure within P4VP(DBSA)x block. In all cases, we found that birefringent can be only found in copolymer with their comb content exceeding 63 wt%. In the thermal analysis, shows us that the glasses transition temperature(Tgs) of the P4VP(DBSA)x block increases with the increasing DBSA content, a result related to the stiffening of the P4VP main chain due to dense packing. On the mesomorphic nanoscale, wide-angle X-ray diffraction study suggests an ordered supramolecular layer structure was formed in most of the complexation cases, in which the thicknesses of the polymer and surf layers were determined from the one-dimensional correlation function. The result indicates that both layers thickness increase with increasing DBSA amounts due to the stretching of the long alkyl tail in DBSA. Finally, macroscopic morphology varied with the DBSA content according to TEM results.