To investigate the role of polyoxovanadates in network connectivity, two new organic-inorganic hybrid vanadates with three-dimensional entangled coordination frameworks, namely [Cu-2(biim)(3)V4O12] 1 and [Co-2(biim)(3)V4O12]center dot 4H(2)O 2 have been synthesized and characterized by infrared (IR), thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. Crystal data for compound 1: triclinic, P-1, a 9.504( 2), b 10.650(2), c 11.993( 2) angstrom; a 72.13(3), angstrom 76.02(3), gamma 65.40(3)degrees; V 1041.4(4) angstrom(3), Z 2, R(final) 0.0492. Crystal data for compound 2: triclinic, P-1, a 9.037( 3), b 10.577(2), c 11.9470( 2) angstrom; a 87.80( 3), beta 81.71( 3), 85.29( 3)degrees; V 1125.8( 4) angstrom(3), Z 1, R(final) 0.0774. Compound 1 is a three-dimensional inclined hetero-catenated framework designed from two two-dimensional sub-layers, [Cu(biim) V4O12] and [Cu( biim)(2)]. Compound 2 is a rare case of a self-catenated 'ilc' network that displays an unusual 4(24) center dot 5 center dot 6(3) topology with the binuclear {Co2O4N6} units as eight-connected nodes.