X-ray absorption spectroscopy (XAS) provides impeccable insight into local solvation structure in the vicinity of the chromophore. Soft-XAS has been used as a direct probe of microheterogeneity in aqueous acetonitrile solutions and has revealed the contrasting nature between weak ammonia/water and strong ammonium/ water hydrogen bonds. X-ray absorption fine-structure (XAFS) spectroscopy was also recently applied to study the hydration structure about ions of all of the first row transition metal elements. As the application of XAS-related methods becomes more ubiquitous, it is increasingly important that theoretical methods meet the challenge of modeling XAS in liquid phase to aid in spectral assignments and to shed light on the atomistic structural details that lead to key spectroscopic signatures.