Langmuir-Blodgett (LB) films of sodium 2-sulfanato-fatty acid higher alkyl esters (n = 12, 14, 16, and 18) were successfully fabricated by the polyion complex technique. Spectroscopic analysis by Fourier transform infrared absorption spectroscopy and X-ray diffraction showed that all polyion-complexed LB films have a well-ordered structure, in which the hydrocarbon chains were tilted at about similar to 7-10 degrees from the surface normal. Furthermore, it was found from the measurement of contact angle that the chain-terminating methyl groups of hydrocarbon chains were closely packed at the surface of the LB film.