Details of the first-shell water structure about Ag+ are reported from a corefinement of the K- and L-2-edge multiple scattering signal in the X-ray absorption fine Structure (XAFS) spectra Detailed fits of the Ag K-edge data that include the contributions from multiple scattering processes in the hydrated ion structure cannot distinguish between models containing tetrahedral symmetry versus those containing collinear O-Ag-O bonds. However, we show that the multiple scattering oscillations at the L-2-edges have distinctly different phase and amplitude functions than at the K-edge. These phase and amplitude functions depend not only oil the symmetry of the multiple scattering paths but also Oil the nature of the final state electronic wave function probed by the dipole-allowed transition. Hence the multiple scattering portions of K- and L-2-edge spectra provide independent measurements of the local symmetry-not it redundant measurement as is commonly believed Oil the basis of the enhanced information content obtained by the Simultaneous assessment of both the K- and L-2-edges, we report that the hydrated Ag+ structure contains five or six water molecules ill the first shell with it significant number of nearly collinear and 90 degrees O-Ag-O bond angles. Finally, the K- and L-2-edge spectra ire used to benchmark the hydration structure that is generated from both DFT-based and classical molecular dynamics simulations. Simulated first-shell structures are compared to the experimental structures.