A new organometallic complex, Co(CO)(2)(NOBuNC)-Bu-t, was synthesized and investigated by photoelectron spectroscopy (PES) and threshold photoelectron photoion coincidence (TPEPICO) spectrometry in order to determine its ionization energy as well as the bond energies in the ionic forms. The assignment of the nine peaks in the PES was based on Kohn-Sham molecular orbital energies, and an adiabatic ionization energy of 7.30 +/- 0.05 eV was determined. In the TPEPICO experiment, the following 0 K onsets were determined for the various fragment ions: (CoCONOBuNC+)-Bu-t (8.17 +/- 0.05 eV); (CoNOBuNC+)-Bu-t (9.01 +/- 0.05 eV); and (CoBuNC+)-Bu-t (10.42 +/- 0.05 eV). Because the photon source did not extend above 14 eV, we could not observe the bare Co+ ion in the experiment. The heat of formation of the (CoBuNC+)-Bu-t ion was estimated by ab initio and DFT calculations of the CoL+ + (BuNC)-Bu-t -> (CoBuNC+)-Bu-t + L (L = CO, NO, NH3, H2O, PMe3) substitution enthalpies.