Two　compounds　of　molybdate　with　2,2＇-bipy　and　[MoO3]:[(2,2＇-bipy)2　(MoO3)3]n　(I)　and　[(2,2＇-bipy)(MoO3)]n　(II)　were　successfully　synthesized　by　hydrothermal　synthesis　method　with　programmable　temperature　control.　In　order　to　clarify　the　relationship　between　the　structure　and　spectroscopy　of　these　two　compounds,　both　of　them　were　characterized　by　means　of　X-ray　powder　diffraction　(XRD),　Fourier　transform　infrared　spectra　(FTIR),　thermal　perturbation　2D-IR　correlation　spectrum　(2D-IR　COS),　thermogravimetric　analysis　(TGA),　scanning　electron　microscopy　(SEM),　High　temperature　infrared　analysis,　UV-Vis　DRS　adsorption　spectra　and　solid　fluorescence　spectrum　to　investigate　the　relationship　between　structure　and　properties　of　the　title　compounds.　The　powder　XRD　patterns　of　the　complexes　are　well　matched　with　the　simulation　based　on　single-crystal　analysis,　which　indicate　that　compound　I　and　II　are　in　a　pure　phase.　The　characteristics　of　vibration　frequency　of　FTIR　and　thermal　perturbation　relative　spectral　response　of　2D-IR　peak　is　consistent　with　the　compound　I　and　II　structure　analysis.　The　synchronous　and　asynchronous　correlation　2D-IR　spectra　of　compounds　also　identified　the　compounds　I　and　II　molybdenum-oxygen　cluster　skeletons　sequencing　of　vibration　intensity　change　with　temperature　consistent　with　the　high　temperature　infrared　analysis.　Through　the　TGA　and　high　temperature　infrared　analysis　it　was　found　that　the　decomposition　temperature　was　more　than　300°C　and　maximum　weight　losses　rates　above　800°C,　which　suggest　that　they　have　good　thermal　stability.　According　to　the　UV-Vis　DRS　spectrum　of　the　compound　I　and　II　there　exists　a　wide　ultraviolet　absorption　band　in　a　range　of　225　to　350　nm.　The　compound　Iand　IIsteady-state　fluorescence　spectrum　under　the　excitation　of　277　and　295　nm　respectively　revealed　compound　I　and　II　have　the　strongest　emission　peak　at　460　and　480　nm　respectively.　This　paper　illustrates　the　coordination　situation　of　these　two　compounds,　and　reveals　the　inherent　law　of　valence　electrons　in　molecule　energy　level　transition.　In　the　meantime　it　was　verified　that　the　weak　interaction　not　only　plays　a　role　of　stability　in　the　frame　of　the　structure　of　the　complexes,　but　also　plays　an　important　role　in　heat　resistance.