The He(I) photoelectron (PE) spectra of cycloheptatriene (1), 7-methylcycloheptatriene (2), 7-methoxycycloheptatriene (3), 7-methylthiocycloheptatriene (4), and 7-diemthylaminocycloheptatriene (5) were recorded and interpreted using MO energies and ionization potentials acquired from B3PW91 calculations. Partial simulated PE spectra were in good agreement with the experimental results. The axial and equatorial conformers have distinct PE spectra as illustrated by simulation. The PE spectra of 2, 3, and 5 are representative of the equatorial conformers, while the PE spectrum of 4 was in accord with a 1:1 mixture of equatorial and axial conformational isomers based on spectral simulation. The calculated free energy differences between the equatorial and axial conformers are in the order of 2 kcal mol–1 (1 cal = 4.184 J) for compounds 2, 3, and 5, where the equatorial conformational isomer is lowest in energy. In the case of 4, the equatorial conformer was only marginally lower in energy than its axial counterpart, where the free energy difference is 0.1 kcal mol–1.Key words: 7-substituted cycloheptatrienes, He(I) photoelectron spectroscopy, B3PW91, spectral simulation.