Designing highly active Keggin-anion anchored on pz-based frameworks is desirable but still a huge challenge. Herein, three new POM-based inorganic–organic hybrid compounds [{Ag5(pz)7}(BW12O40)] (1), [{Ag5(pz)7}(SiW12O40)](OH)·H2O (2), (Hpyr)[{Ag(pz)}2(PMo12O40)] (3) (pz = pyrazine, pyr = pyrrole) have been fabricated via a hydrothermal synthesis method. All compounds were characterized by elemental analyses, infrared spectroscopy (IR), powder X-ray diffraction (PXRD), thermogravimetric (TG), scanning electron micrographs (SEM), and transmission electron microscope (TEM). Single-crystal X-ray diffraction displays that the configurations of compounds 1 and 2 are parallel. In compound 1, the [BW12O40]5– is as 8-connected node incorporated into the orifice of the Ag-pz framework forming the glamorous POM-based metal organic frameworks (POMOFs). And the 3D POMOFs possess a kind of novel topology {42·54}2{44·512·68·73·9}{44·53·63}{44·55·6·74·9}{73}. There is a metal–organic nanotube structure constructed by fo...