The Langmuir film behavior of fluorine-containing side chain liquid crystal copolysiloxanes at the air-water interface has been studied over a temperature range of 277.5-310 K. The surface pressure-area isotherms exhibited a transition from an expanded to a condensed phase. In the expanded phases the main chains of the polymers were anchored at the air-water interface. In the condensed phases the extension or partial exclusion of the main chains at the air-water interface was mainly controlled by the cross-sectional area of the side chain. The transferred Langmuir-Blodgett (LB) multilayer did not give any X-ray diffraction peak. With heating, a molecular ordering of the LB film was induced so that the film showed the Bragg diffraction peak.