Poly(4-vinylpyridine) derivatives alkylated with dimethylsulfate, octylbromide and dodecylbromide were synthesized. Bromide anions in the polymer salts were substituted with octylsulfate, dodecylsulfate or bis(2-ethylhexyl)sulfosuccinate (AOT) anions using ion-exchange reactions. The small-angle X-ray scattering (SAXS) studies of the structure of the comb-like polysalts demonstrated their highly-ordered structure. Loading the comb-like polycation with the surfactant anions leads to additional ordering of the polysalts structure. in the case of large AOT anions the transition from lamella to hexagonal structure is observed. Polyelectrolyte - surfactant complexes (PEC) of poly(4-vinyl-1-methylpyridinium) cation with octylsulfate and dodecylsulfate counter ions demonstrate a higher degree of order than the comb-like polymers having a similar chemical structure. The SAXS studies were complemented by dynamic light scattering study of the solutions of the polymers in chloroform. In the solution the comb-like polymers and their complexes with linear surfactants have coil conformations with the size of the coils close to that of the original poly-4-vinylpyridine. The conformations of PECs with octylsulfate and dodecylsulfate counter ions are more unfolded than those of the corresponding comb-like polymers. (C) 2009 Elsevier Ltd. All rights reserved.