Two novel two-dimensional organic-inorganic hybrid vanadium tellurites M(phen)V2TeO8 (M = Cu (1), Ni (2)) have been hydrothermally synthesized and characterized by the elemental analyses, IR spectra, EPR spectrum, XPS spectra, TG analyses, and single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic system, space group P2(1)/c, with a = 9.2193(18) Angstrom, b = 7.9853(16) Angstrom, c = 21.401(4) Angstrom, beta = 97.54(3)degrees, and Z = 4. Compound 2 crystallizes in the monoclinic system, space group P2(1)/c, with a = 9,2163(18) Angstrom, b = 7.9897(16) Angstrom, c = 21.386(4) Angstrom, beta = 97.52(3)degrees, and Z = 4. Compounds 1 and 2 are isostructural, and both exhibit interesting two-dimensional networks with [V2TeO8](infinity) double-chain-like ribbons bridged by metal-organic complex moieties [M(phen)](2+) (M = Cu and Ni). Furthermore, the three-dimensional supramolecular architectures of compounds 1 and 2 are formed by pi-pi stacking interactions of phen groups between adjacent layers.