We present infrared photodissociation spectra of [Ni(CO2)(n)](-) clusters (n = 2-8) in the wavenumber region of 1000-2400 cm(-1) using the antisymmetric stretching vibrational modes of the CO2 units in the clusters as structural probes. We use density functional theory to aid in the interpretation of our experimental results. The dominant spectral signatures arise from a core ion composed of a nickel atom and two CO2 ligands bound to the Ni atom in a bidentate fashion, while the rest of the CO2 molecules in the cluster play the role of solvent. Other core structures are observed as well but as minor contributors. The results for [Ni(CO2)(n)](-) clusters are discussed in the context of other anionic transition- metal complexes with CO2.