By utilizing symmetrical pentacarboxylate ligands, 3,5-di(2',5'-dicarboxylphenyl)benzoic acid (H5L1) and 3,5-di(2',4'-dicarboxylphenyl)benzoic acid (H5L2), two novel porous Zn-MOFs, [Zn5(μ3-H2O)2(L1)2]·3DMA·4H2O (CTGU-3) and [Zn3(μ3-OH)L2(H2O)3]·H2O (CTGU-4) have been synthesized under solvothermal conditions. CTGU-3 and CTGU-4 exhibit 3D microporous frameworks with flu and dia topologies and possess unique secondary building units [Zn5(μ3-H2O)2(RCO2)6] and [Zn3(μ3-OH)(RCO2)3], respectively. Such porous systems create a unique space or surface to accommodate Ag nanoparticles (Ag NPs), which could efficiently prevent Ag NPs from aggregation and leaching. In this work, two new Ag@Zn-MOF composites, denoted as Ag@CTGU, have been successfully fabricated through solution infiltration, for the reduction of nitrophenol. Compared with CTGU-4, CTGU-3 shows enhanced catalytic efficiency toward the reaction when it is used as a catalyst support of Ag NPs. Moreover, gas sorption and luminescence properties of two compounds were also investigated.