The copolymerization of aryl bis‐ and tris‐trifluorovinyl ether monomers yields aromatic perfluorocyclobutyl (PFCB) polymers, via thermally initiated step‐growth cycloaddition chemistry. PFCB polymers and their copolymers enjoy a unique combination of attributes well suited for applications in photonic technologies, such as broad tailorability of refractive indices and thermo‐optic coefficients, low transmission losses at 1300 and 1550 nm, high thermal, mechanical, and optical stability, and excellent melt and solution processability. Planar PFCB structures can be processed by direct micro‐transfer molding, which is a first step towards rapid soft‐lithographic fabrication of polymer planar lightwave circuits. Copolymerization chemistry and processing parameters and characterization, including thermal (Tg = 120–350 °C) and optical properties (refractive indices from 1.443 to 1.508 at 1550 nm; thermo‐optic coefficients dn/dT = –7×10–5 K–1 to –1.5 × 10–4 K–1), birefringence (< 0.003), and temporal stability of refractive index, are described.