Fluorine-containing polymers were synthesized using three main synthetic approaches: First, polyamic acid (PA-1) and polyimide (PI-1) were produced from direct polycondensation of 4,4‘-hexafluoroisopropylidenediphthalic anhydride and 4,4‘-hexafluoroisopropylidenedianiline in N-methyl-2-pyrrolidinone (NMP). Second, a novel polyester (PEMPFTDE) with fluorine side chains was synthesized from poly(maleic anhydride-co-ethylene). Finally, novel fluorine-containing acrylate (PTFPM) was synthesized by bulk and gas-phase polymerizations. Novel monolayer and ultrathin films of the polymers were prepared by the Langmuir−Blodgett technique. They formed a stable monolayer. The collapse pressure of PA-1 was 62 mN/m, and the area per repeat unit (RU) was 0.12 nm2. The PI-1 has a collapse pressure of 60 mN/m with an area per RU of 0.23 nm2. PI-1 films formed a stable monolayer, too. Multilayer depositions onto substrates were possible for all of the polymers except for PEMPFTDE. LB films were characterized by infrared (...