High resolution variable energy photoelectron spectra using synchrotron radiation, of valence, inner valence, and core levels of gas phase heavy metal carbonyl compounds [e.g. W(CO)(6), Re(CO)(5)X (X = Cl, Br, Re(CO)(5)] are reported. The high resolution (0.1 eV) metal 4f core level spectra show, for the first time, vibrational splitting. In addition, ligand field broadening is shown to be an important contributor to the 4f linewidth, especially for Os(CO)(5). The greatly improved resolution also provides much narrower 4f shake-up peaks in W(CO)(6) than have been observed with laboratory X-ray sources. The complete inner valence spectra are interpreted using the inner valence spectrum of CO and the only previously reported complete inner valence spectrum of a metal carbonyl [Cr(CO)(6)]. The variable energy of synchrotron radiation is especially important for assigning the valence metal d orbitals [in, for example, CpM(CO)(3), M = Mn, Re] using the enhancement of metal d cross sections after the excitation of the core p orbitals.