We present a structural investigation of thin films of diblock copolymers PS-P4VP in which 4VP forms an ionic bond with a sterically demanding surfactant, bis (2-ethylhexyl) sulfosuccinate acid (AOT). The results depend strongly on the interplay between microphase separation and surfactant ordering. Protonation of the P4VP homopolymer or diblock PS-b-P4VP with AOT leads to a multilayer structure in which the surfactant determines the layer thickness. In thin films of the protonated block copolymer, the segregation between the blocks generates nanostructures with an in-plane periodicity defined by the molecular masse of the copolymer and the stoichiometry of the complex. Variation of the composition of the blocks and the molar ratio AOT/pyridine leads to structural transitions: cylinders of (AOT/P4VP) -> lamellae -> cylinders of PS. Remarkably, regardless of the morphology, the bcp microdomain structure remains orthogonal to the air substrate interface. Finally, we show that hydrolysis of AOT results in the formation of pores with a variable geometry useful for templating two-dimensional inorganic structures.