A series of novel trifunctional and tetrafunctional trifluorovinyl aryl ether monomers and perfluorocyclobutane (PCFB) aromatic ether polymers have been synthesized and characterized. These PFCB polymers exhibit desirable properties for low loss optical waveguide applications. Monomers used in this study were prepared from the key intermediate, 4-bromophenyl trifluorovinyl ether. Through thermal dimerization of the aromatic trifluorovinyl ether moieties, these monomers can be either melt or solution polymerized to form PFCB-containing prepolymers with good processability for the fabrication of optical waveguides. After a post-thermal cross-linking process, the resulting thermosets possess low optical loss (0.30 dB/cm at 1310 nm with 1% of DR-1 doping), high thermal stability (T-g: 85-350 degreesC), good solvent resistance, and low surface roughness.