We study small titanium oxide-CO2 cluster anions in vacuo to understand the fundamental interactions between TiOx and CO2 in the presence of an excess electron. Infrared spectra of [TiOx(CO2)(y)](-) (x = 1-3, y > 1) were obtained using photodissociation spectroscopy and assigned through quantum chemistry calculations, identifying the formation of carbonato, oxalato, oxo, eta(2)-(O,O), and carbonyl ligands in the core ions of these clusters, with carbonato ligands being the dominant ligand species.