Well-defined dinuclear silver(I) complexes have been targeted for applications in catalysis and materials chemistry, and the effect of close silver-silver interactions on electronic structure remains an area of active inquiry. In this study, we describe the synthesis, structure, and photophysical properties of dimeric silver complexes featuring a redox-active naphthyridine diimine ligand. Unusually for silver(I), these complexes display absorption features in the visible region due to metal-metal to ligand charge transfer (MMLCT) transitions, which arise from the combination of close silver-silver interactions and low-lying ligand pi* orbitals. The complexes' photophysical properties are explored via a combination of spectroscopic and computational studies, revealing MMLCT excited state lifetimes that exceed 1 mu s. These results portend previously unforeseen applications of silver(I) dimers in visible light absorption and excited state reactivity.