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Photoelectron spectroscopy employing synchrotron radiation is applied to learn about the electronic structure of regio-regular poly(3-hexyl-thiophene) (P3hT). We study the valence band photoelectron spectra around the carbon 1s threshold. This technique is equivalent to resonant excitation of core electrons into empty valence states. We probe the properties of these carriers in the conduction band and also learn about valence band states involved in the carbon (K L L) Auger transitions. The data give evidence that monomeric orbital energies are dominating in such processes. We conclude that poly(3-hexyl-thiophene) is a polymer with a rather short conjugation length.