Structural parameters of the Sr2+ and, for the first time, of the EU2+ ions in nonaqueous solutions were determined by the X-ray absorption fine structure (XAFS) method and compared with those of the aqua ions. For both Eu2+ and Sr2+ ions, a decrease in coordination number (N) and metal-to-solvent distances was found along the increasingly solvating MeCN < H2O much less than DMF < DMSO solvent series: for strontium, N = 8 with [Sr(MeCN)(8)](2+) (2.665(6) Angstrom) and [Sr(H2O)(8)](2+) (2.600(3) Angstrom) and N = 7 with [Sr(DMF)(7)](2+) (2.555(5) Angstrom) and [Sr(DMSO)(7)](2+) (2.540(7) Angstrom); for europium(II), N = 8 with [Eu(MeCN)(8)](2+) (2.640(4) Angstrom), N = 7 with [Eu(H2O)(7)](2+) (2.584(5) Angstrom), and N = 6 with [Eu(DMF)(6)](2+) (2.54](3) Angstrom) and by extrapolation [Eu(DMSO)(6)](2+) (2.525 Angstrom). Smaller coordination numbers are observed for the EU2+ ion in O-coordinating solvents. The ionic radii of both Sr2+ and EU2+ ions are very similar, but the slightly softer character of the Eu2+ ion leads to shorter M-N and longer M-O bonds.