A　series　of　supermolecules　of　PWxV12-x-MV(　PWxV12-x:　polyoxometalates　x　=　2,　4,　6,　8,　10;　MV:　methyl　violet)　with　Keggin　structure　were　prepared　and　their　characters　were　studied　by　electronic　spectra,　infrared　spectra　and　fluorescence　spectra.　As　a　result,　the　supermolecules　were　formed　by　the　cooperating　action　between　polyoxometalates　and　methyl　violet.　In　the　supermolecule,　the　structures　of　cation　and　anion　are　not　destroyed.　With　the　content　of　V　increasing,　the　oxidation　ability　of　polyoxometalates　anion　is　enhanced,　and　the　interaction　of　methyl　violet　cation　and　polyoxometalates　anion　is　enhanced　too.　The　FTIR　absorption　peaks　of　nu(as)(Mdouble　bondO(t)),　nu(as)(M-O-b-M)　and　nu(as)(M-O-c-M)　move　from　966,　886,　and　804　cm(-1)　to　955,　875　and　786　cm(-1),　respectively;　the　UV-Vis　absorption　peak　moves　from　519　to　506　run;　the　emission　peak　excited　at　530　nm　moves　from　692　to　644　nm　too.　These　changes　are　according　with　the　degree　of　the　interaction　of　polyoxometalates　and　methyl　violet.