Abstract: Binuclear transition metal carbonyl clusters serve as the simplest models in understanding metal-metal and ligand bonding that are important organometallic chemistry catalysis. Binuclear first row transition metal carbonyl ions are produced via a pulsed laser vaporization/supersonic expansion cluster ion source in the gas phase. These ions are studied by mass-selected infrared photodissociation spectroscopy in the carbonyl stretching frequency region. Density functional theory calculations have been performed on the geometric structures and vibrational spectra of the carbonyl ions. Their geometric and electronic structures are determined by comparison of the experimental IR spectra with the simulated spectra. The structure and the metal-metal and metal-CO bonding of both saturated and unsaturated homonuclear as well as heteronuclear carbonyl cluster cations and anions are discussed.