Vibrationally resolved C1s and S2p photoelectron spectra of the thiophene molecule have been recorded using monochromated synchrotron radiation at photon energies of 330 eV and 210 eV, respectively. The photoelectron bands contain complex vibrational structures which are analyzed using ab initio and curve-fitting procedures. The analysis is in good agreement with the experimental spectrum which enables identification of two chemically shifted carbon 1s core hole states. We were also able to determine the molecular-field splitting of the S2p(3/2) ionic state to about 99 meV. The molecular-field splitting was moreover calculated using second-order Moller-Plesset perturbation theory, confirming the result from the fitting procedure.