In this article, we study the photoinduced dissociation pathways of a metallocarbonyl, Os-3(CO)(12), in particular the consecutive loss of CO groups. To do so, we performed photoelectron-photoion coincidence (PEPICO) measurements in the single ionization binding energy region from 7 to 35 eV using 45-eV photons. Zero-energy ion appearance energies for the dissociation steps were extracted by modeling the PEPICO data using the statistical adiabatic channel model. Upon ionization to the excited ionic states above 13 eV binding energy, non-statistical behaviorwas observed and assigned to prompt CO loss. Double ionization was found to be dominated by the knockout process with an onset of 20.9 similar to 0.4 eV. The oscillator strength is significantly larger for energies above 26.6 similar to 0.4 eV, corresponding to one electron being ejected from the Os3 center and one from the CO ligands. The cross section for double ionization was found to increase linearly up to 35 eV ionization energy, at which 40% of the generated ions are doubly charged.