Naphthalene and Si based trifluorovinyl ether monomers were synthesized in two or three steps for thermoplastic and thermoset PFCB poly aryl ethers, respectively. Crosslinked PFCB polymers were preared in the neat without the need for a catalyst or initiator by thermal 2 π + 2 π cyclopolymerization, and showed excellent solvent resistance for solution processable OTFTs. Perfluorocyclobutane(PFCB) based crosslinked polymers were studied as gate dielectrics for organic thin film transistors (OTFTs).