The functional nanofilms of poly(3,4-ethylenedioxythiophene) - poly(styrenesulfonate) (PEDOT:PSS) anionic complex were prepared on the transparent substrates by layer-by-layer (LBL) assembly with N-cetylpyridinium bromide (CPB) as cationic surfactant. It has studied dependence of films thickness on the number of bilayers of PEDOT:PSS/CPB and on initial concentration of PEDOT:PSS in colloid solution. The LBL films of PEDOT:PSS/CPB demonstrate the thermal sensitivity of optical absorption in visible and near IR range of spectrum which promises their application in sensor devices.