Two inorganic-organic hybrid compounds with the formula M(4,4'-bipy)(H2O)V2Se2O10 (M = Co, Ni) were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compounds Co(4,4'-bipy)(H2O)V2Se2O10 (1) and Ni(4,4'-bipy)(H2O)V2Se2O10 (2), which are structural analogues, crystallize in the triclinic space group P (1) over bar with crystal data a = 7.9665(3) Angstrom, b = 8.1974(3) Angstrom, c = 13.8096(4) Angstrom, alpha = 85.704(2)degrees, beta = 73.5180(10)degrees, gamma = 75.645(2)degrees, V = 837.76(5) Angstrom(3), and Z = 2 and a = 7.9489(19) Angstrom, b = 8.128(2) Angstrom, c = 13.709 Angstrom, alpha = 85.838(6)degrees, beta = 73.736(8)degrees, gamma = 75.594(9)degrees, V = 823.5(4) Angstrom(3), and Z = 2, respectively. [M(4,4'-bipy)-(H2O)V2Se2O10] (M = Co, Ni) have a three-dimensional structure and consist of two subunits, [(VO2)(SeO3)]infinite chains and [M(4,4'-bipy)(H2O)](2+) fragments. The [(VO2)(SeO3)](-) chains are composed Of [V2Se4O14](4-) clusters linked by VO4N triangular bipyramids. The 4,4'-bipy molecule as a bifunctional organic ligand is directly linked to Co or Ni and V atoms, affording the three-dimensionality. The compounds were characterized by infrared spectroscopy and differential thermal and thermogravimetric analyses.