The solution behavior of stoichiometric complexes from poly(a-methylstyrene)-block-poly(N-ethyl-4-vinypyridinium) cations (PMeS-b-PE4VP) and bis(2-ethylhexyl)sulfonsuccinate (AOT) anions in a variety of organic solvents with low polarity is characterized. These complexes as well as the stoichiometric complexes between homopolymer poly(N-ethyl-4-vinypyridinium) cations (PE4VP) and AOT were soluble in most common organic solvents except aliphatic hydrocarbons. Both PMeS-b-PE4VP- and PE4VP-based complexes dissolve in hexane in the presence of small amounts of mixed methanol-ethyl ether cosolvent. The PMeS-b-PE4VP/AOT complex forms stable micelle-like aggregates with an effective diameter of ca. 70 nm under these conditions. Such aggregates are not observed in the solutions of the PE4VP/AOT complex, PMeS segments in the PiMeS-b-PE4VP/AOT complex segregate into an insoluble core, while the PE4VP segments bound with AOT stabilize these particles in solution. Such a type of morphology has not been described and is unique for polymer-surfactant complexes.