The Langmuir monolayer behavior of (di)alkoxy-substituted precursor poly(p-phenylenevinylenes) (PPVs) with a methoxy-leaving group was studied. The average orientation of the aromatic ring and the ether groups at the air-water interface was elucidated by external F-T-infrared reflection spectroscopy measurements at the air-water interface combined with FT-IR computer simulations. The aromatic rings of the precursors, except those of the dibutoxy-substituted one, take on, directly after spreading, an almost perpendicular orientation to the water subphase. The isotherms of these precursors showed no special transitions, and these polymers can be considered to be in a condensed or 2-D collapsed state with lateral cohesive. pi-pi interactions between the aromatic rings as the most prominent interaction leading to this condensed state. The aromatic rings of the dibutoxy-substituted precursor are lying flat at the water surface at large areas per repeating unit and can be considered to be in the expanded state directly after spreading. The isotherm of this precursor showed two transitions because here the chain conformation is predominantly determined by the butyl chains and not by the main chain.