Surface pressure-area (pi-A) isotherms of monolayers of amphiphilic precursor polymer(p-xylene-bis-tetrahydrothiopenium salt) with heptadecafluorooctanesulfate (HFOS), stearic acid and arachidic acid as counterions were investigated. A stable Langmuir film was formed by spreading a mixture of ethanol and 1,1,1-trichloroerhar.e (1:1) of HFOS anion on an aqueous subphae containing an ionic poly(p-phenylenevinylene) (PPV) precursor polymer with opposite charge. It was shown by Fourier transform infrared spectroscopy that Langmuir-Blodgett (LB) films of PPV precursor polymer were conposed of p-xylene-bis-tetrahydrothiopenium salt polymer complexed with counterions such as HFOS. It was also confirmed with UV-visible absorption spectroscopy that multilayer LB films of PPV precursor polymer were well-formed at molecular level. Surface morphologies of the PPV precursor polymer LB films transferred at different surface pressures to a mica were also studied with atomic force microscopy.