H2S-Ag-I was synthesised by a laser-ablation technique and characterised, both by ab initio calculations at the CCSD(T)(F12*) level of theory and by rotational spectroscopy. The configuration at S is rigidly pyramidal, with no inversion on the microwave timescale. The experimental geometry [r(0)(S-Ag) = 2.4228(18) angstrom, r(0)(Ag-I) = 2.5416(9) angstrom, phi(0) = 78.94(7)degrees] is in good agreement with that [r(e)(S-Ag) = 2.417 angstrom, re(Ag-I) = 2.554 angstrom, phi(e) = 77.0 degrees] calculated ab initio. The angular geometry of H2S-Ag-I is isomorphic with those of other members of the series H2S-Ag-X and with their hydrogen-bonded and halogen-bonded analogues H2S center dot center dot center dot HX and H2S center dot center dot center dot XY, respectively. (C) 2012 Elsevier B.V. All rights reserved.