The results of experimental studies of the valence electronic structure of 1-butene employing photoelectron spectroscopy as well as electron momentum spectroscopy are interpreted on the ground of quantitative calculations of one-electron and shake-up ionization energies and of the related Dyson orbitals, using one-particle Green's function theory in conjunction with the third-order algebraic diagrammatic construction scheme (ADC(3)). Comparison is made with simulations of (e, 2e) electron momentum distributions obtained from standard (B3LYP) Kohn–Sham orbitals. Our analysis is based on highly quantitative determinations of the energy difference between the cis and gauche (C1) conformers, within ∼0.02 kcal mol−1 accuracy, and a thermostatistical evaluation thereby of conformer weights beyond the level of the rigid rotor harmonic oscillator approximation. Relative entropies are found to be particularly sensitive to hindered rotations. The shake-up onset is located at 15.9 eV, and the orbital picture of ionization breaks down completely at electron binding energies above 19 eV. If the available experimental momentum profiles demonstrate the dominance of the C1 conformer, they are in this case clearly not sensitive enough to the molecular conformation for evaluating conformer abundances with accuracies better than 10% due to the limited energy and momentum resolutions and likely physical complications.