Luminescent metal–organic frameworks (MOFs) are appealing. In this regard, the dye molecule 1,2,4,5-tetra(4-pyridyl)benzene (bztpy), a tetradentate ligand, can be rationally incorporated for the modulation of structures and photochemical properties as a building unit. By reacting bztpy and K[Ag(CN)2] in the presence of CuCl in a solution of NH3·H2O/EtOH at room temperature, we managed to synthesize two novel MOFs exhibiting good luminescent behavior. In the reaction, CuCl was proven to be important as a catalyst, which enables the reactant to generate reactive intermediate [Ag(NH3)2]Cl with the help of ammonia. Thus, Ag+ ions released from intermediate promote the formation of products 1 and 2. Transformation between two compounds can be realized by simple operations. Topology studies reveal that 1 belongs to a 4-fold interpenetrating “moganite” net, but for 2 a new-found (3,4)-connected net occurred with a Schläfli symbol of {62.104}{62.10}2. Photoluminescent behaviors of solid 1 and 2 exhibit intense emission with λemmax at ca. 538 and 547 nm, respectively, mainly assigned to intraligand transition. On the basis of the facts above, the use of dye molecules into MOFs provides the way to modulate photochemical properties.