X-ray absorption near-edge structure (XANES) spectroscopy has been used, in conjunction with extended X-ray absorption fine structure (EXAFS), to determine the coordination structure of the Ag+ ion in a dimethyl sulfoxide (DMSO) solution. From the EXAFS data analysis, the Ag-O first shell distance in DMSO was found to be 2.31(3) Å, with 4.1(5) oxygen atoms surrounding the Ag+ ion, in fair agreement with previous results. This technique did not allow us to determine the geometry of the 4-fold coordination complex and a quantitative analysis of the XANES region was carried out to shed light on this issue. The XANES data analysis confirmed the presence of a four-coordinated complex, unambiguously showing that a regular tetrahedral [Ag(DMSO)4]+ complex is formed when silver triflate is dissolved in DMSO solution.