Structural parameters of the Sr2+ and, for the first time, of the Eu2+ ions in aqueous solution were determined by the XAFS method. For the Sr2+, the use of an improved theoretical approach led to a first shell coordination number of 8.0 (3), a Sr-O distance of 2.600 (3) Angstrom and a Debye-Waller factor of sigma(2) = 0.0126 (5) Angstrom(2). These results were confirmed by an analysis performed with experimental phase and amplitude, extracted from the solid reference compound [Sr(H2O)(8)](OH)(2). The same theoretical approach was used for the analysis of the Eu2+ XAFS spectra in aqueous solution. This gives a first coordination shell of Eu2+ formed by 7.2 (3) water molecules, an Eu-O distance of 2.584 (5) Angstrom, and a high Debye-Waller factor of sigma(2) = 0.0138 (5) Angstrom(2). Whereas Eu3+ occurs as an equilibrium between the [Eu(H2O)(8)](3+) and the [Eu(H2O)(9)](3+) occurs in aqueous solution as an equilibrium between a predominant [Eu(H2O)(7)](2+) ion and a minor [Eu(H2O)(8)](2+) species.