The reaction between MB-DIPY sodium salts and Ag(i) ions results in the formation of unprecedented MB-DIPY2Ag2 dimers in both solution and the solid state. These dimers have a short Ag-Ag contact (∼2.9 Å) and orthogonal twist in each of the MB-DIPY chromophores. The electronic structure of the unique dimers was probed by spectroscopic and theoretical methods.