A new neutral [Ag2（Hida）（NH3）2] molecule （1, H3ida = 1H-imidazole-4,5-dicarboxylic acid） has been synthesized and structurally characterized by single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 18.3928（8）, b = 8.3299（5）, c = 13.682（7） A, β = 113.179（2）°, V = 1926.9（10）A^3, Z = 8 and Dc = 2.784 g·cm^-3. In the solid state, this disilver（I） compound can aggregate to furnish the energetically stable ligand-unsupported Ag^I-Ag^I interaction concomitant with significant photoluminescence changes in different aggregate states, and such argentophilicity interaction is also supported by molecular orbital calculations.
