Four　novel　polyoxovanadium　borates　with　[(VO)12O6B18O42],　namely　(enH2)6H3　[(VO)12O6B18O42]　·　13H2O(1),　[Ni(en)2]6H3　[(VO)12O6B18O42]　·　8H2O(2),　[Cu(en)2]5H3　[(VO)12O6B18O42]　[B(OH)3]2　·　16H2O(3)　and　(enH2)4Na4H3　[(VO)12O6B18O42]　·　8H2O(4),　were　synthesized.　The　relationship　between　their　properties　and　structures　were　studied　by　using　FTIR,　UV-Vis　DRS　and　fluorescence　etc.　Among　these　compounds,　compound　(1)　possesses　isolated　[(VO)12O6B18O42]　cage,　there　is　a　ring　of　B18O42　sandwiched　between　two　vanadium-oxygen　clusters　V6O18　by　eighteen　B-(μ3-O)-V　bonds,　while　compound　(2)　is　rather　six　[Ni(en)2],　each　connected　with　the　Bi18O42　ring　by　two　Ni-(μ3-O)-B.　In　compounds　(3)　and　(4),　the　anion　clusters　[(VO)12O6　B18O42]13-　are　connected　with　[Cu(en)2]2+　and　Na+,　respectively.　Thus,　the　compounds　(3)　and　(4)　are　extended　to　an　infinite　two-dimensional　network　structure,　respectively.　These　characteristic　vibrational　frequencies　of　polyoxovanadium　borates　are　related　to　the　structures　of　these　compounds.　In　UV/Vis　DRS　spectra,　there　are　two　characteristic　peaks　of　polyoxometalates　at　205　and　260　nm,　respectively.　The　fluorescence　spectra　of　these　four　compounds　have　been　studied,　and　they　have　emission　peaks　at　415　nm　excited　by　310　nm　which　are　caused　by　Oμ→Mo.　The　fluorescence　lifetimes　of　these　compounds　have　been　studied.