Four novel supramolecular compounds based on Keggin phosphomolybdate and different organocations: (H(2)bpy)(1.5)[PMo12O40]center dot 1.5H(2)O 1, (H(2)bpi)(Hbpi)[PMo12O40] 2, (H(2)bbi)(Hbpi)[PMo12O40] 3, (H(2)bbi)(Hbbi)[PMo12O40] 4, (bpy = 4,4'-bipyridine, bpi = 1,1'-(1,3-propanediyl)bis(imidazole), bbi = 1,1'-(1,4-butanediyl)bis(imidazole)) have been hydrothermally prepared and characterized by elemental analysis, IR, TG, XRD and single-crystal X-ray diffraction. Crystal data analysis revealed that all the compounds are composed of discrete organonitrogen cations and [PMo12O40](3-) polyanions and exhibits interesting supramolecular frameworks from one to three dimensions via electrostatic and hydrogen bond interactions. Additionally, their electrochemical characters, electrocatalytic behaviors and solid state fluorescent properties at room temperature have been investigated in detail. (C) 2013 Elsevier B.V. All rights reserved.