Reactions of a tetravanadate anion, [V4O12](4-), with a series of lanthanide(III) salts yield three types of lanthanide complexes of macrocyclic polyoxovanadates: (Et4N)(6)[Ln(III)V(9)O(27)] [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6)] (Et4N)(5)[(H2O)Ho-III(V4O12)(2)] (7), and (Et4N)7[Ln(III)V(10)O(30)] [Ln = Er (8), Tm (9), Yb (10), Lu (11)] Lanthanide complexes 1-11 are isolated and characterized by IR, elemental analysis, single-crystal X-ray diffraction, and extended X-ray absorption fine structure spectroscopy (EXAFS). Lanthanide complexes 1-6 are composed of a square-antiprism eight-coordinated Lnill center. with a macrocyclic polyoxovanadate that is constructed from nine VO4 tetrahedra through vertex sharing. The structure of 7 is composed of a seven-coordinated Ho-III center, which exhibits a capped trigonal-prism coordination environment by the sandwiching of two cyclic tetravanadates with a capping H2O ligand. Lanthanide complexes 8-11 have a six-coordinated Lnill center with a 10-membered vanadate ligand. The structural trend to adopt a larger coordination number for a larger lanthanide ion among the three types of structures is accompanied by a change in the vanadate ring sizes. These lanthanide complexes are examined by EXAFS spectroscopies on lanthanide L-III absorption edges, and the EXAFS oscillations of each of the samples in the solid state and in acetonitrile are identical. The Ln-O and Ln ...V bond lengths obtained from fits of the EXAFS data are consistent with the data from the single-crystal X-ray studies, reflecting retention of the structures in acetonitrile.