A　series　of　vanadium　selenites　covalently　bonded　with　metal-organic　complex,　namely,　Ni(2,2-bipy)(2)V2O4(SeO3)(2)　(1),　cu(2,2-bipy)V2O4(SeO3)(2　center　dot)0.5H(2)O　(2)　and　Cu-2(2,2-bipY)(2)V5O12(SeO3)(2)　(3)　(2,2-bipy=2,2-bipyridine)　have　been　hydrothermally　synthesized　and　structurally　characterized.　They　exhibit　three　different　structural　dimensions,　from　OD　cluster,　1D　chain　to　2D　layer.　Compound　1　features　a　OD　{Ni(2,2-bipy)(2)V2O4(SeO3)(2))(2)　dimeric　cluster　composed　of　two　{Ni(2,2-bipy)(2)}(2+)　moieties　connected　by　the　{V4O8(SeO3)(4)}(4-)　cluster.　Compound　2　shows　a　1D　{cu(2,2-bipy)V2O4(SeO3)(2)}(n)　chain　in　which　the　{Cu-2(2,2-bipy)(2)}(4+)　moieties　are　bridged　by　the　{V4O8(SeO3)(4)}(4-)　clusters.　Compound　3　displays　a　2D　structure　consisted　of　mixed　valence　vanadium　selenites　layers　{(VV4Se2O18)-V-IV-Se-V-O-IV}(n)(4-)　and　{Cu(2,2-bipY)}(2+)　complex　moieties.　The　adjacent　layers　are　further　interconnected　via　pi-pi　interactions　between　the　2,2-bipy　ligands　exhibiting　an　interesting　3D　supramolecular　architecture.　Both　compound　I　and　2　contain　a　new　{V4O8(SeO3)(4)}(4-)　cluster　and　compound　3　exhibits　the　first　2D　vanadate　polyhedral　layer　in　vanadium　selenites/tellurites　with　organic　moieties.　(C)　2016　Elsevier　Inc.　All　rights　reserved.