By introducing the isomeric pyridyltetrazole into POMs, four POM-templated MOFs compounds, H[Ag₆(2-pytz)₄(H₂O)₄][PW₁₂O₄₀]·6H₂O (1), [Ag₃(3-pytz)₂]₂[AgPW₁₂O₄₀] (2), H[KAg₇(4-pytz)₅][SiW₁₂O₄₀] (3), {H[NaAg₇(4-pytz)₅(H₂O)_0.5][GeMo₁₂O₄₀]}₂ (4) [pytz = 5-(pyridyl) tetrazolate], were hydrothermally synthesized and characterized by routine methods and single-crystal X-ray crystallography. Due to 2-pytz as a bridging linker and chelator, compound 1 displays a 2D MOF with a void (ca. 19.1 × 8.8 Å), in which the Keggin anions as sandwich templates locate in the adjacent two voids. In 2, 3-pytz as a shorter radiating linker generates a compacted 2D MOF, in which the Keggin anions as chain templates direct the formation of a stair-like MOF. In the isostructural compounds 3 and 4, 4-pytz as the bridging and radiating linkers form 3D covalent MOFs with larger voids (ca. 25.3 × 12.5 Å), in which the Keggin anions as double-templates occupy the voids in a “shoulder-to-shoulder” mode. In addition, the photoluminescence of the compounds were investigated.