Two new three-dimensional (3D) coordination compounds, namely a lead(II) coordination polymer (CP) {[Pb3(µ5-cpta)(µ6-cpta)(phen)2]·2H2O}n (1) and a zinc(II) metal-organic framework (MOF) {[Zn2(µ4-cpta)(µ-OH)(µ-4,4′-bipy)]·6H2O}n (2), were hydrothermally assembled from 2-(5-carboxypyridin-2-yl)terephthalic acid (H3cpta) as an unexplored principal building block and aromatic N,N-donors as crystallization mediators. Both products were isolated as air-stable microcrystalline solids and were fully characterized by IR spectroscopy, elemental and thermogravimetric analysis, and powder and single-crystal X-ray diffraction. Structural and topological features of CP 1 and MOF 2 were analyzed in detail, allowing to identify a topologically unique 4,5,5,6-connected net in 1 or a very rare 4,4-connected net with the isx topology in 2. Thermal stability and solid-state luminescent behavior of 1 and 2 were also investigated. Apart from revealing a notable topological novelty, both compounds also represent the first structurally characterized Pb(II) and Zn(II) derivatives assembled from H3cpta, thus opening up the application of this unexplored pyridine-tricarboxylate block in the design of new metal-organic architectures. © 2018 by the authors. Licensee MDPI, Basel, Switzerland.