||Polymers containing fluorine have several advantages such as high thermal stability, chemical resistance and low dielectric constant. Among them, perfluorocyclobutane (PFCB) ring contaning polymers can be applied to plastic optical fibers and waveguides due to optical transparency and good mechanical properties. Azobenzene is a well known photoactive chromophore, which undergoes photoinduced and thermal cis-trans isomerization. In this research, a PFCB fluoropolymer containing azobenzene groups was synthesized and characterized for photonic applications for combination of the merits of PFCB fluoropolymers and photoactivity of azobenzenes. The themal properties were characterized with TGA and DSC. Surface relief grating (SRG) and photo-induced orientation were formed by exposure to argon ion laser beams. The formation of SRG was investigated by measuring diffraction efficiencies and surface modulation depth was measured by AFM.