The photochemistry of 2-trifluoromethylnorbornene in pentane solution has been investigated. Direct photolysis with 193 nm light yields 1-trifluoromethyl-2-norcarene in 90% yield, due to formal [1,3]-sigmatropic rearrangement, in addition to three other minor products. Chlorobenzene-sensitized photolysis affords photoreduction products, principally exo- and endo-2-trifluoromethylnorbornane and decane isomers, in addition to several products of higher molecular weight. On the basis of comparisons of the photochemistry of this compound to that previously reported for norbornene and 2-cyanonorbornene, as well as spectroscopic evidence, it is suggested that the lowest excited singlet state (the photoreactive state in solution) in 2-trifluoromethylnorbornene is the π, π* state. The results indicate that trifluoromethyl substitution has the effect of significantly raising the energy of the π,R(3s) Rydberg state in simple alkenes, without altering the high energy (ca. 6.5 eV) or the localized character of the alkene π, π* state. Furthermore, they lend additional support to the view that the carbene-derived products typically formed upon photolysis of alkenes in solution are derived from π,R(3s) excitation. Keywords: Rydberg, photolysis, far-uv, alkene, solution phase, singlet, triplet.