Poly(4-vinylpyridinium) bromides containing octyl and dodecyl pendant groups were synthesized. Bromide anions in these polymer salts were substituted with dodecylsulfate and bis(2-ethylhexylsuccinate) anions using ion-exchange reactions. Initially, P4VP and its derivatives loaded with hydrophobic groups were deposited on a mica surface from diluted solutions in chloroform for visualization. Images of single adsorbed macromolecules were obtained using scanning force microscopy. Original P4VP chains form partially compacted self-intersecting coils. Loading the polymer chains with large hydrophobic groups and especially the increase in the number of alkyl tails (see Figure) per monomer unit of the polymer chain leads to the stretching of the coils, and the comb-like macromolecules adopt more and more extended self-avoiding 2D conformations when deposited on the substrate.