A novel organic-inorganic hybrid material [Ag(DPPE)2]2[Mo4O10(CH3O)6]·2CH3OH (1) has been prepared by using [Mo4O10(CH3O)6]2- in polyoxometalate (POMs) as inorganic building block, 1,2-bis(diphenylphosphine)ethane (DPPE) as an organic ligand and silver nitrate as a silver source, through the means of a combination of solvothermal and conventional synthesis and via the self-assembly process. X-ray single crystal diffraction analysis shows that compound 1 is formed by electrostatic interaction with polyanion [Mo4O10(CH3O)6]2- and [Ag(DPPE)2]+ cationic units. In addition, the structure of the compound was analyzed by X-ray powder diffraction and fourier transform infrared spectroscopy. The stability was determined by thermogravimetric analysis, the band gap was determined by solid UV-visible diffuse reflection test, and the fluorescence spectra in methanol solution were measured. It was found that compound 1 showed good photocurrent response.