We report here the first measurements of the complete valence shell binding energy spectra and the outer valence orbital momentum profiles of thiophene, using a high resolution binary (e, 2e) electron momentum spectrometer, at an impact energy of 1200 eV plus the binding energy and using symmetric non-coplanar kinematics. Binding energy spectra of the complete valence shell have been obtained. The summed experimental momentum profile of the HOMO la, and NHOMO 3b(1) is compared with the theoretical momentum distributions calculated using Hartree-Fock and density functional theory methods with various basis sets. The experimental measurement is well described by the calculations. (C) 2004 Elsevier B.V. All rights reserved.