Two novel inorganic–organic hybrids [Co(H 2 O)(2,2′-bipy)V 2 O 6 ] (1) and [Ni(H 2 O)(2,2′-bipy)V 2 O 6 ] (2) have been prepared in 70–78% yields by the hydrothermal reactions of V 2 O 5 , LiOH·H 2 O, 2,2′-bipyridine (2,2′-bipy), MSO 4 ·xH 2 O (M=Co, x=7, 1; M=Ni, x=6, 2), and H 2 O carried out in Teflon-lined autoclaves at 160 °C for 96 h. The new solids have been characterized by single crystal X-ray structure analyses, manganometric titration, elemental and thermogravimetric analysis, and IR spectroscopic studies. The isomorphous structures of 1–2 are comprised of {M/V/O} layers-perpendicular to the b-axis- composed of corner-sharing {VO 4 } tetrahedra and {CoN 2 O 4 } octahedra. The mixed-metal oxide layers contain [V 2 O 6 2− ] n motifs made up of corner-sharing {VO 4 } tetrahedra. The 2,2′-bipyridyl groups, bonded to the M centers in the layers, are projecting outward to occupy regions in between the successive metal oxide layers. Crystal data: 1, C 10 H 10 CoN 2 O 7 V 2 , orthorhombic space group Pca2(1),a=9.1870(4),b=10.5451(5),c=14.3487(6)Å, V=1390.07(11)Å 3 , Z=4, ρ calc =2.059Mgm −3 , R 1 =0.0167; 2, C 10 H 10 NiN 2 O 7 V 2 , orthorhombic space group Pca2(1),a=9.1445(4),b=10.5076(5),c=14.3123(6)Å, V=1375.22(11)Å 3 , Z=4, ρ calc =2.081Mgm −3 , R 1 =0.0214.