An assembly of Keggin polyoxomolybdate and organic substrate (Hbipy) 3 [PMo 12 O 40 ] (1, bipy=2,2′-bipyridine) was synthesized and characterized by elemental analysis, infrared spectrum, and single-crystal X-ray analysis. The ligand bipy of compound 1 was generated by a decarboxylation coupling reaction of H 2 pdc (H 2 pdc=pyridine-2,6-dicarboxylic acid) in situ under hydrothermal reaction conditions and the control experiments illustrate that La(NO 3 ) 3 or Ce(NO 3 ) 3 , which does not appear in the final structure, is necessary for the decarboxylation coupling reaction. Moreover, compound 1 displays strong photoluminescence property in the solid state at room temperature.