The decay of core-excited electronic states in free 1,3 trans butadiene molecules has been studied using high-resolution synchrotron radiation and electron spectrometry. The core-level energy Shift between the terminal and central carbon atoms is 0.64 eV making selective excitation of core electrons from these atoms possible. Resonant excitation to the a(u)(pi*) valence state leads to autoionizing decay channels which proceed according to the atomic site in the molecule. The radiationless decay is localized, and certain molecular orbitals are excluded from the decay depending upon the site of the core hole. This phenomenon is confirmed by semiempirical INDO calculations based upon the equivalent core approximation. The vibrational structure of the resonances below the carbon K edge has been measured and fit to extract vibrational energies and intensities, chemical shifts, and the lifetimes of the centrally and terminally excited states. The C Is spectrum is also measured with vibrational resolution and the energies of the normal vibrational modes are extracted. The bond lengths are derived by application of a linear coupling analysis.