We report on characteristic effects of monolayers from polyelectrolytes (PEs) complexed by oppositely charged small surface-active counterions. Two different methods of monolayer preparation are compared in detail (counterion spread on PE, method 1; PE spread on counterion solution, method 2). Both methods lead to different monolayer characteristics. It could be demonstrated that the unconventional way of method 2 results in highly unfolded states of the PE and should therefore be preferred for the reported types of systems; loops and tails of the polymer as the predominant result of method 1 are avoided by this method. For the first time reliable data are presented that during PE-surfactant compression well-ordered triple-layer states are formed, which could quantitatively be transferred. with perfect Y-type behaviour. Quartz crystal microweighing and ellipsometry were mainly used as characterization methods.