Three new products, [Cu2(μ3-dppa)(2,2′-bipy)2(H2O)]n·2nH2O (1), [Co4(μ4-dppa)2(phen)4(H2O)4]·2H2O (2), and [Co2(μ6-dppa)(μ-4,4′-bipy)(H2O)2]n·3nH2O (3) were synthesized using a hydrothermal method from Cu(II) and Co(II) metal(II) chlorides, 3-(3,4-dicarboxyphenoxy)phthalic acid (H4dppa), and different auxiliary ligands, namely 2,2′-bipyridine (2,2′-bipy),1,10-phenanthroline (phen), and 4,4′-bipyridine (4,4′-bipy). Products 1–3 were characterized by elemental analysis, FTIR, TGA, PXRD, SEM, and single-crystal X-ray crystallography. The structure of 1 features a 1D chain of the 2C1 topological type. Compound 2 shows a discrete tetrameric complex. Product 3 demonstrates a 3D metal–organic framework (MOF) with the new topology. Their structure and topology, thermal stability, and catalytic activity were studied. In particular, excellent catalytic activity was demonstrated for copper(II)-polymer 1 in the cyanosilylation reaction at 35 °C.