Novel fluorinated main-chain liquid-crystalline/crystalline polymers were prepared through thin film polymerization to investigate the effect of -(C6F4)- on the surface free energy. The fluorine in the phenyl rings does not lower the total surface free energy of the thin copolymer films, compared to those without fluorine. Interestingly, the Lewis acid components (gamma (+)) of the surface free energy of the fluorine-containing polymers increase with an increase in the -(C6F4)-content, indicating the increasing electron accepting character of the surface.