Medium energy ion scattering (MEIS), using 100 keV H+ incident ions, has been used to investigate the structure of the Ag(1 1 1)(√7 × √7)R19° –CH3S surface phase. The results provide the first direct evidence that this structure does involve substantial reconstruction of the Ag surface layer. The measured absolute scattered ion yields and blocking curves are in generally good agreement with a specific structural model of the surface based on a reconstructed layer containing 3/7 ML Ag atoms, previously suggested on the basis of scanning tunnelling microscopy (STM) and normal incidence X-ray standing wave (NIXSW) studies. However, the MEIS data indicate that any rumpling of the thiolate layer, is small, and probably ⩽0.2 Å. This value is smaller than the amplitude suggested in the STM and NIXSW studies, but could be entirely consistent with the earlier experimental data.