Four new organic–inorganic hybrid compounds based on bicapped Keggin polyoxometalate {PMo12Sb2O40}: [H24,4′-bpy][PMo12Sb2O40]·6H2O (1), [Him]2[PMo12Sb2O40]·H2O (2), [H3(DABCO)2][PMo12Sb2O40]·2H2O (3) and [Mn(phen)3][PMo12Sb2O40] (4) (bpy = bipyridine, im = imidazole, DABCO = 1,4-diazabicyclo[2,2,2]octane, phen = phenanthroline) have been prepared hydrothermally and characterized by IR, UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), powder XRD analyses, elemental analyses, fluorescence analysis and single crystal X-ray diffraction analyses. The four compounds are new examples of hybrid compounds based on bicapped Keggin polyoxometalate {PMo12Sb2O40}. Compound 1, 2 and 3 are constructed from {PMo12Sb2O40} anions and different organic moieties, respectively. Compound 4 is formed by combining {PMo12Sb2O40} anions and manganese coordination complexes.Graphical abstractFour new members of the family of compounds based on {PMo12Sb2O40} polyoxometalate have been synthesized and characterized by IR, XPS, XRD, fluorescence analyses, elemental analyses and single-crystal X-ray diffraction analyses.Highlights► Four supramolecular hybrids based on {PMo12Sb2O40} polyanions. ► Three supramolecular hybrids based on {PMo12Sb2O40} and different organic ligands. ► One supramolecular hybrid based on {PMo12Sb2O40} and manganese coordination complexes. ► Supramolecular hybrids based on different hydrogen bonding interactions.