A series of bis(thienyl)ethenes (BTEs) possessing perfluorocyclopentene backbones and methoxymethyl groups (MOM) in the 2/2′-positions of the thiophenes was prepared and examined. The substitution pattern of the 5/5′-positions was varied, covering the range from electron-donating to electron-withdrawing. The substituent effects of the absorption wavelengths of the ring-opened and the ring-closed isomers, which are interconverted by reversible 6π-electrocyclizations and cycloreversions, are studied by means of the spectroscopic Hammett equation and the Hammett–Brown equation. Excellent correlations of these linear free energy relationships were found, when the σ_p values of the Hammett equation, which summarize inductive, mesomeric and field effects, were replaced to the Hammett–Brown σ_p⁺ and σ_p⁻ values which also take direct conjugation into account. We studied solvent effects on the spectroscopic properties and embedded the BTEs into polymethylmethacrylate (PMMA) coatings to examine their fatigue resistance. By our studies, the spectroscopic properties of BTEs can be adjusted by variation of the substitution pattern to a desired excitation wavelength for switching processes.