Valence and inner-shell (C 1s ) electronic excitation spectra of norbornene, 2-methylnorbornene, and 2-trifluoromethylnorbornene have been measured by electron energy loss spectroscopy. These data have been complemented with gas- and solution-phase UV absorption spectra in the 5–6.7 eV range, HeI UV photoelectron spectra, and AM1 semi-empirical calculations for the three compounds. The valence shell energy loss and UV absorption spectra show marked variations throughout the series of compounds, suggesting the presence of at least three low-lying electronic excited states. The spectral bands have been assigned as due to π,R(3s), π,π*, and π, R(3p) excitations on the basis of their term values and the differences between their intensities in the solution and gas phase absorption spectra. The valence shell spectra indicate that while the vertically-excited π,R(3s) state is substantially lower in energy than the (vertically-excited) π,π* state in norbornene and the 2-methyl derivative, they are nearly isoenergetic in 2-trifluoromethylnorbornene. This difference in excited state manifolds is reflected in profound differences between the solution phase photochemistry of norbornene and the 2-trifluoromethyl derivative.The carbon 1s spectra are even more sensitive to substituent than the valence shell energy loss spectra. An interpretation is proposed which reflects the spatially localized character of inner-shell excitation and a "group orbitals" picture of the unoccupied MO's as accessed by C 1s excitation. Keywords: Rydberg, electron energy loss, UV absorption, UV photoelectron spectroscopy, alkene, gas-phase.