Two　compounds　of　organic　molybdate-alkali　salt:　[H(4,4＇-bipy)](2)　[K2Mo8O26]　(I)　and　H-3　[Na　Mo8O26](4,4＇-bipy)(5)　(H2O)(4)　(II),　with　beta-[Mo8O26](4-)　anion,　were　synthesized.　The　relationship　between　their　properties　and　structures　was　studied　by　using　FTIR,　Raman,　NIR-Vis　and　fluorescence　etc.　They　possess　isolating　beta-[Mo8O26](4-)　anion,　whose　terminal　O　atoms　combine　with　alkali.　The　FTIR　and　Raman　spectra　showed　that　the　vibrational　frequencies　of　the　group　are　related　to　the　structure　of　the　materials.　In　UV-Vis　spectra　of　compound　(I)　and　(II),　there　is　a　characteristic　wide　peak　at　280-300　nm.　The　fluorescence　spectra　of　compound　(I)　and　(II)　were　studied,　which　showed　that　the　wide　emission　peak　is　from　450　to　650　nm　and　excited　by　350　nm　for　compound　and　the　emission　peak　is　from　400　to　550　nm　and　excited　by　325　run　for　compound　(II).　For　compound　(I),　the　intensity　of　emission　becomes　stronger　with　decreasing　of　temperature,　and　so　does　the　fluorescence　lifetime.