A series of 19 p-substituted aromatic trifluorovinyl ether compounds were prepared from versatile intermediate p-Br-C6H4-O-CF=CF2 and underwent thermal radical mediated cyclodimerization to new difunctional compounds containing the 1,2-disubstituted perfluorocyclobutyl (PFCB) linkage. The synthetic scope demonstrates the functional group transformation tolerance of the fluorovinyl ether, and the dimers are useful as monomers for traditional step-growth polymerization methods. F-19 NMR spectra confirmed that p-substitution affects the trifluorovinyl ether group chemical shifts. The first kinetic studies and substituent effects on thermal cyclodimerization were performed, and the results indicated that electron-withdrawing groups slow the rate of cyclodimerization. The data were further analyzed using the Hammett equation, and reaction constants (F) of -0.46 at 120 degrees C and - 0.59 at 130 degrees C were calculated. This study presents the first liner free energy relationship reported for the cyclodimerization of aromatic trifluorovinyl ethers to PFCB compounds.