An unusual heterobimetallic bis(triphenylphosphane)(NO)Ag-Co(dimethylglyoximate)(NO) coordination compound with both bridging and terminal -NO (nitro) coordination modes has been isolated and characterized from the reaction of [CoCl(DMGH)(PPh)] (DMGH is dimethylglyoxime or N,N'-dihydroxybutane-2,3-diimine) with excess AgNO. In the title compound, namely bis(dimethylglyoximato-1κO,O')(μ-nitro-1κN:2κO,O')(nitro-1κN)bis(triphenylphosphane-2κP)cobalt(III)silver(I), [AgCo(CHNO)(NO)(CHP)], one of the ambidentate -NO ligands, in a bridging mode, chelates the Ag atom in an isobidentate κO,O'-manner and its N atom is coordinated to the Co atom. The other -NO ligand is terminally κN-coordinated to the Co atom. The structure has been fully characterized by X-ray crystallography and spectroscopic methods. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) have been used to study the ground-state electronic structure and elucidate the origin of the electronic transitions, respectively.