The structures of solvated complexes of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and In(III) ions in 1,1,3,3-tetramethylurea (TMU) have been determined by means of EXAFS (extended X-ray absorption fine structure) and electronic spectroscopy. The solvation structures in TMU are square pyramidal for the Mn(II) and Ni(II) ions, distorted tetrahedral for the Co(II) and Cu(II) ions, tetrahedral for the Zn(II) ion, and octahedral for the Cd(II) and In(III) ions, while in water all these metal ions are six-coordinated octahedrons. The solvation structure of Fe(II) ion is square pyramidal or trigonal bipyramidal. In the bulky TMU solvent, the coordination number should be reduced for relaxation of the sterically repulsive interaction around the solvated metal ions. The metal-oxygen (M-O) bond lengths of solvated metal ions in TMU are 209 +/- 1, 205 +/- 1, 200 +/- 1, 200 +/- 1, 192 +/- 1, 195 +/- 1, 228 +/- 1, and 213 +/- 1 pm for Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and In(III) ions, respectively. The M-O bond lengths for Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) ions in TMU are shorter than those of corresponding metal(II) ions in water, while the M-0 bond lengths in TMU and water are the same for the six-coordinate Cd(II) and In(III) ions.