Summary: A novel crosslinkable dendritic polymer has been synthesized by the thermal polymerization of peripheral aryl trifluorovinyl ether moieties of a highly fluorinated dendrimer. The resulting perfluorocyclobutane(PFCB)‐containing dendritic polymer exhibited excellent processability, low optical loss (0.36 dB · cm−1 at 1 310 nm with 1% dye doping), high thermal stability, and good solvent resistance for waveguide‐based photonic applications.