Some applications of XAFS to solutions of simple metal complexes and simple inorganic species were studied. XAFS for simple 3d-transition metal complexes in aqueous media were analyzed, which indicate what information is included in XAFS about the bonding. Solvent effects on XAFS were also studied for anionic chelate complexes, bromide ion, and triiodide ion in a variety of solvents. Distances from the central metal to nearest neighbors of anionic chelate complexes were varied with solvents in accord with the blue shift of the UV-vis. spectra. Distances and their coordination numbers of bromine-solvents in the nearest neighbor as well as of the iodine-iodine bond in the triiodide ion were also varied. For both solute, the solvent effects should be classified with the solvent proticity. Some of these solvent effects can be interpreted with donor-acceptor solvent parameters. These analyses exemplify XAFS can be applied to solution samples not only as a structural tool but for characterizing solute species.