The solvothermal reactions of tetrazole- and pyridyl-containing asymmetric amide ligands [N-(pyridin-3-yl)isonicotinamide (PIA) and 3-(1H-tetrazole-1-acetic acid amido)pyridine (TAAP)] with Zn(NO3)2 in the presence of [Mo7O24]6− anions lead to the formation of two new compounds, namely H4[(Mo8O26)(PIA)2]·H2O (1) and H4[Zn2(TAAP)4(H2O)4](Mo8O26)2·16H2O (2), which have been characterized by single-crystal X-ray diffraction, IR spectra, elemental analysis, TGA and PXRD analysis. Compound 1 is a 3D supramolecular structure derived from the 0D [(Mo8O26)(PIA)] cluster containing MoN bond. Compound 2 features a two-fold interpenetrating 3D network with [Mo8O26]4− anions as templates and possess 4-connected lvt net. Furthermore, the electrochemical, photocatalysis and luminescent properties of compound 2 have been investigated.